CN111717939B - Narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof - Google Patents
Narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof Download PDFInfo
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Abstract
The narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide is divided into an inner layer and an outer layer, wherein the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 The specific surface area of the whole precursor secondary spherical particles is 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particles both contain three elements of nickel, cobalt and aluminum, and the inner layer of the precursor is of a loose structure with a large specific surface area, so that when the anode material is sintered with a lithium source, the lithium source can be rapidly and uniformly diffused to the inner core, the sintering efficiency of the anode material is improved, and the production cost is reduced; a preparation method of nickel-cobalt-aluminum hydroxide with narrow distribution and large particle size overcomes the defect that a precursor synthesized by a solid phase method cannot reach the uniformity of an atomic layer, and overcomes the defect that aluminum hydroxide flocculent precipitate generated in the synthesis process of a conventional liquid phase method is generated to obtain the precursor with a double-layer structure with a loose inner layer and a tight outer layer.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a narrowly-distributed large-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 atom-level uniformity, and the performance is difficult to fully exert.
Chinese patent CN108767256a discloses a method for preparing a nickel cobalt lithium aluminate precursor as a battery cathode material, wherein the nickel cobalt lithium aluminate precursor is prepared by roasting with aluminum nitrate, so that the situation 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 tap 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 that firstly, a nickel-cobalt-aluminum precursor is prepared by adopting a chemical coprecipitation method, and then the precursor and lithium salt are calcined to obtain an NCA material; the solubility product constant of aluminum hydroxide is 1.3 multiplied by 10 -33 And nickel hydroxide and cobalt hydroxide (divalent) are each 2X 10 -15 And 1.6X 10 -15 The 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.
With the continuous improvement of the requirement of the new energy field on the energy density of the cathode material, the mole percentage of Ni in the nickel-cobalt-aluminum cathode material is gradually increased from 80% to 88% or more, however, the improvement of the Ni content makes the cycle performance of the cathode material a short plate restricting the application of the cathode material, and in order to improve the cycle performance of the nickel-cobalt-aluminum cathode material, the consistency of the cathode material can be improved by preparing a narrowly distributed nickel-cobalt-aluminum precursor with uniform particle size and good sphericity.
Meanwhile, with the increase of D50, in the sintering process of the cathode material, since the diffusion path of the lithium source from the outside to the inside of the precursor becomes long, it becomes difficult to achieve rapid and uniform distribution of the lithium source in the precursor, and although this problem can be solved by prolonging the sintering time or by adopting a multi-sintering method, there are multiple problems of reduced production efficiency, high production cost, and the like.
Disclosure of Invention
The invention aims to provide a precursor of a nickel-cobalt-aluminum hydroxide with narrowly distributed large particle size as an active material of a nickel-cobalt-aluminum acid lithium battery positive electrode material, wherein secondary spherical particles of the precursor are divided into an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 The specific surface area of the whole precursor secondary spherical particles is 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel in the total molar content of the metal 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 9.0-20.0 mu m, the secondary spherical particles can be used as the anode material of the lithium battery, the energy density and the cycle performance of the battery can be further improved, the inner layer of the precursor is of a loose structure with a large specific surface area, and when the anode material is sintered with a lithium source, the lithium source can be conveniently and uniformly diffused to the inner core, the sintering efficiency of the anode material is improved, and the production cost is reduced.
The second purpose of the invention is to provide a preparation method of the narrowly distributed large-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 synthesis process of the conventional liquid phase method on the other hand, so that the precursor with a double-layer structure with a loose inner layer and a tight outer layer is obtained, and the precursor also has the characteristics of good sphericity, 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 narrowly distributed large-particle-size nickel cobalt aluminum hydroxide which is spherical or spheroidal particles, the particles consist of an inner layer and an outer layer, the inner layer is loose, the outer layer is tight, and the specific surface area of the inner layer is 18-30 m 2 G, and the specific surface area of the whole particles is 7 to 15m 2 (iv) g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel in the total molar content of the metal is 85% -98%; the particles have the characteristic of narrow distribution, wherein K90= (D90-D10)/D50 is less than or equal to 0.90, and D50 is 9.0-20.0 μm.
The D50 of the inner layer of the narrowly distributed nickel-cobalt-aluminum hydroxide with large particle size is 3.0-14.0 mu m.
The invention provides a preparation method of a narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, which comprises the following steps:
step 1, 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 nickel-cobalt mixed salt solution by using nickel and cobalt soluble salts as raw materials and pure water;
step 3, preparing a sodium hydroxide solution;
step 4, preparing an aluminum alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution;
step 5, preparing an ammonia water solution;
step 6, selecting ammonia water and ammonium salt to prepare an ammonia-ammonium solution;
step 7, 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 8, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water solution prepared in the step 5 to form a bottom solution for starting up the reaction;
step 9, adding the nickel-cobalt-aluminum mixed salt solution, the sodium hydroxide solution and the ammonium hydroxide solution into a reaction kettle in a concurrent flow manner for reaction, and controlling the temperature, the pH value, the ammonia concentration and the like; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 3.0-14.0 mu m;
step 10, adding a nickel-cobalt mixed salt solution, an aluminum-alkali mixed solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in a parallel flow manner for reaction, and controlling the temperature, the pH value, the ammonia concentration and the like;
step 11, stopping all feeding when detecting that the D50 of the materials in the reaction kettle reaches 9.0-20.0 mu m;
and 12, washing and drying the slurry obtained in the step 11, and then sequentially sieving and demagnetizing to obtain the narrowly distributed large-particle-size nickel cobalt aluminum hydroxide.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 1, soluble salts of nickel, cobalt and aluminum are one or more of chloride, nitrate and sulfate.
In the preparation method of the narrowly distributed large-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 narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 2, the soluble salt of nickel and cobalt is one or more of chloride, nitrate and sulfate.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 2, the total molar concentration of nickel-cobalt metal ions in the mixed salt solution is 1.0-2.5 mol/L.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, the molar concentration of the prepared sodium hydroxide solution is 4.0-11.0 mol/L in step 3.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 4, 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 large-particle-size nickel-cobalt-aluminum hydroxide, the concentration of the prepared ammonia water is 6.0-12.0 mol/L in the step 5.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 6, the ammonia concentration of the prepared ammonia-ammonium solution is 2.0 mol/L-15.0 mol/L, and the mass ratio of the ammonia water to the ammonium salt is 10.
In the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 8, the pH value in the base solution is 10.8-11.4, and the ammonia concentration is 2.0-10.0 g/L.
In the step 9, the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is 10.8-11.4, and the ammonia concentration is 2.0-10.0 g/L.
In the step 10 of the preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, the reaction temperature in a kettle is controlled to be 45-65 ℃, the pH value is controlled to be 10.8-11.4, and the ammonia concentration is controlled to be 8.0-14.0 g/L.
The invention has the beneficial effects that:
the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide has moderate particle size, specific surface area and good layered structure with less impurities, can be used as a precursor of an active substance of a nickel-cobalt lithium aluminate battery positive electrode material, secondary spherical particles of the precursor are divided into an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 The specific surface area of the whole precursor secondary spherical particles is 7 to 15m 2 (iv) g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel in the total molar content of the metal is 85% -98%; the secondary spherical particles of the precursor have the characteristic of narrow distribution, K90= (D90-D10)/D50 is less than or equal to 0.90, and D50 is 9.0-20.0 mu m, the secondary spherical particles can be used as the positive electrode material of the lithium battery, the energy density and the cycle performance of the battery can be further improved, the inner layer of the precursor is of a loose structure with a large specific surface area, and when the positive electrode material is sintered with a lithium source, the lithium source can be conveniently and uniformly diffused to the inner core, the sintering efficiency of the positive electrode material is improved, and the production cost is reduced; a preparation method of a narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, which overcomes the defect that a precursor synthesized by a solid phase method cannot reachThe atomic level is uniform, on the other hand, the defect of aluminum hydroxide flocculent precipitate generated in the synthesis process of the conventional liquid phase method is overcome, a precursor with a double-layer structure with a loose inner layer and a tight outer layer is obtained, the precursor also has the characteristics of good sphericity, stable structure and high consistency, the principle of nucleation and crystal growth is changed by regulating the adding mode of an aluminum source, a core with a large specific surface area is formed inside particles, a shell with a small specific surface area is formed outside the particles, the lithium source is promoted to be rapidly diffused into the particles in the sintering process, and the uniformity of the material is improved. The narrowly distributed large-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 the nickel-cobalt-aluminum hydroxide, and is particularly suitable for the production process of the nickel-cobalt-aluminum hydroxide with narrow distribution and large particle size.
Drawings
FIG. 1 is a 1000-fold FESEM image of a narrow distribution large particle size nickel cobalt aluminum hydroxide prepared in example 1;
FIG. 2 is a 1000-fold FESEM image of the narrowly distributed large particle size nickel cobalt aluminum hydroxide prepared in example 2;
fig. 3 is a 1000-fold FESEM image of the narrow distribution large particle size nickel cobalt aluminum hydroxide prepared in example 3.
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 large-particle-size nickel-cobalt-aluminum hydroxide is spherical or quasi-spherical particles, the particles consist of an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 A specific surface area of 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particles both contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel in the total molar content of the metal is 88-90%; the particles have a narrow widthThe distribution is characterized in that K90= 0.65-0.75 and D50 is 11.5 μm; the D50 of the inner layer of the particles was 9.0. Mu.m. And is prepared by the following steps:
step 1, according to the molar ratio of nickel, cobalt and aluminum elements in the required nickel-cobalt-aluminum hydroxide inner layer, namely 89;
step 2, according to the molar ratio of nickel and cobalt elements in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 89, preparing a nickel-cobalt mixed salt solution with the total metal ion concentration of 2mol/L by using nickel and cobalt soluble salts as raw materials and pure water;
step 3, preparing a sodium hydroxide solution with the concentration of 10.0mol/L;
step 4, preparing an aluminum-alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.2mol/L;
step 5, preparing 10.0mol/L ammonia water solution;
step 6, selecting ammonia water and ammonium salt according to the mass ratio of the ammonia water to the ammonium salt of 10;
step 7, 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 8, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water solution prepared in the step 5 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.1, and the ammonia concentration is 7.0g/L;
step 9, adding the nickel-cobalt-aluminum mixed salt solution, the sodium hydroxide solution and the ammonium hydroxide solution into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 55 ℃, the pH value to be 11.1 and the ammonia concentration to be 7.0g/L; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 9.0 mu m;
step 10, adding a nickel-cobalt mixed salt solution, an aluminum-alkali mixed solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 55 ℃, the pH value is controlled to be 11.2, and the ammonia concentration is 9.0g/L;
step 11, stopping all feeding materials when detecting that the D50 of the materials in the reaction kettle reaches 11.5 mu m;
and 12, washing and drying the slurry obtained in the step 11, and sequentially sieving and demagnetizing to obtain the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide.
The FESEM of the prepared sample is shown in figure 1, and the FESEM has good uniformity and dispersibility, basically consistent sample particle size and good sphericity.
Example 2
The narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide is spherical or quasi-spherical particles, the particles consist of an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 A specific surface area of 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the nickel accounts for 91-93 percent of the total molar content of the metal; the particles have the characteristic of narrow distribution, wherein K90= 0.65-0.75, and D50 is 14.0 μm; the D50 of the inner layer of the particles was 7.0. Mu.m. And is prepared by the following steps:
step 1, according to the molar ratio of nickel, cobalt and aluminum elements in the inner layer of the required nickel-cobalt-aluminum hydroxide, namely 92;
step 2, according to the molar ratio of nickel and cobalt elements in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 92, selecting nickel and cobalt soluble salts as raw materials and preparing a nickel-cobalt mixed salt solution with the total metal ion concentration of 1.8mol/L with pure water;
step 3, preparing a sodium hydroxide solution with the concentration of 8.0 mol/L;
step 4, preparing an aluminum-alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.4mol/L;
step 5, preparing 10.0mol/L ammonia water solution;
step 6, preparing an ammonium hydroxide solution by selecting ammonia water and ammonium salt according to the mass ratio of the ammonia water to the ammonium salt of 10;
step 7, 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 8, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water solution prepared in the step 5 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.1, and the ammonia concentration is 5.0g/L;
step 9, adding the nickel-cobalt-aluminum mixed salt solution, the sodium hydroxide solution and the ammonium hydroxide solution into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 50 ℃, the pH value to be 11.1 and the ammonia concentration to be 5.0g/L; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 7.0 mu m;
step 10, adding a nickel-cobalt mixed salt solution, an aluminum-alkali mixed solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in a parallel flow manner for reaction, controlling the reaction temperature in the kettle to be 50 ℃, the pH value to be 11.3 and the ammonia concentration to be 12.0g/L;
step 11, stopping all feeding materials when detecting that the D50 of the materials in the reaction kettle reaches 14.0 mu m;
and 12, washing and drying the slurry obtained in the step 11, and sequentially sieving and demagnetizing to obtain the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide.
The FESEM of the prepared sample is shown in figure 2, and the FESEM has good uniformity and dispersibility, basically consistent sample particle size and good sphericity.
Example 3
The narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide is spherical or spheroidal particles, the particles consist of an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 G, and the specific surface area of the whole particles is 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel to the total mole content of the metal is 94% -96%; the particles have the characteristic of narrow distribution, wherein K90= 0.65-0.90 and D50 is 18.0 μm; the D50 of the inner layer of the particles was 14.0. Mu.m. And is prepared by the following steps:
step 1, according to the molar ratio of nickel, cobalt and aluminum elements in the inner layer of the required nickel-cobalt-aluminum hydroxide, namely 95;
step 2, according to the molar ratio of nickel and cobalt elements in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 95;
step 3, preparing a sodium hydroxide solution with the concentration of 6.0 mol/L;
step 4, preparing an aluminum-alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution, wherein the molar concentration of Al in the aluminum-alkali mixed solution is 0.5mol/L;
step 5, preparing 8.0mol/L ammonia water solution;
step 6, selecting ammonia water and ammonium salt according to the mass ratio of the ammonia water to the ammonium salt of 10;
step 7, 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 8, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water solution prepared in the step 5 to form a base solution for starting up the reaction, wherein the pH value of the base solution is 11.2, and the ammonia concentration is 9.0g/L;
step 9, adding the nickel-cobalt-aluminum mixed salt solution, the sodium hydroxide solution and the ammonium hydroxide solution into a reaction kettle in a concurrent flow manner for reaction, controlling the reaction temperature in the kettle to be 60 ℃, the pH value to be 11.2 and the ammonia concentration to be 9.0g/L; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 14.0 mu m;
step 10, adding a nickel-cobalt mixed salt solution, an aluminum-alkali mixed solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in a concurrent flow manner for reaction, wherein the reaction temperature in the kettle is controlled to be 60 ℃, the pH value is controlled to be 11.2, and the ammonia concentration is 12.0g/L;
step 11, stopping all feeding materials when detecting that the D50 of the materials in the reaction kettle reaches 18.0 mu m;
and 12, washing and drying the slurry obtained in the step 11, and sequentially sieving and demagnetizing to obtain the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide.
The FESEM of the prepared sample is shown in figure 3, and the FESEM has good uniformity and dispersibility, basically consistent sample particle size and good sphericity.
Claims (12)
1. The narrowly distributed nickel-cobalt-aluminum hydroxide with large particle size is characterized in that the narrowly distributed nickel-cobalt-aluminum hydroxide with large particle size is spherical or spheroidal particles, the particles consist of an inner layer and an outer layer, the inner layer is loose, the outer layer is compact, and the specific surface area of the inner layer is 18-30 m 2 A specific surface area of 7 to 15m 2 (ii)/g; the grains of the inner layer and the outer layer of the particle contain three elements of nickel, cobalt and aluminum, wherein the percentage of nickel in the total molar content of the metal is 85% -98%; the particles have the characteristic of narrow distribution, wherein K90= (D90-D10)/D50 is less than or equal to 0.90, and D50 is 9.0-20.0 μm.
2. The narrow distribution large particle size nickel cobalt aluminum hydroxide of claim 1 wherein the D50 of the inner layer of particles is 3.0 μm to 14.0 μm.
3. A preparation method of a narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide is characterized by comprising the following steps:
step 1, 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 nickel-cobalt mixed salt solution by using nickel and cobalt soluble salts as raw materials and pure water;
step 3, preparing a sodium hydroxide solution;
step 4, preparing an aluminum alkali mixed solution by selecting an aluminum soluble salt and a sodium hydroxide solution;
step 5, preparing an ammonia solution;
step 6, selecting ammonia water and ammonium salt to prepare an ammonia-ammonium solution;
step 7, 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 8, adding pure water into the reaction kettle until the pure water overflows the bottom layer stirring paddle, and then adding the sodium hydroxide solution prepared in the step 3 and the ammonia water solution prepared in the step 5 to form a bottom solution for starting up the reaction;
step 9, adding the nickel-cobalt-aluminum mixed salt solution, the sodium hydroxide solution and the ammonium hydroxide solution into a reaction kettle in a parallel flow manner for reaction, and controlling the temperature, the pH value, the ammonia concentration and the like; stopping feeding when the D50 of the materials in the reaction kettle is detected to reach 3.0-14.0 mu m;
step 10, adding a nickel-cobalt mixed salt solution, an aluminum-alkali mixed solution, a sodium hydroxide solution and an ammonia water solution into a reaction kettle in a parallel flow manner for reaction, and controlling the temperature, the pH value, the ammonia concentration and the like;
step 11, stopping all feeding when detecting that the D50 of the materials in the reaction kettle reaches 9.0-20.0 mu m;
and 12, washing and drying the slurry obtained in the step 11, and sequentially sieving and demagnetizing to obtain the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide.
4. The method for preparing nickel cobalt aluminum hydroxide with narrow distribution and large particle size according to claim 3, wherein in step 1 and step 2, the soluble salts of nickel, cobalt and aluminum are one or more of chloride, nitrate and sulfate.
5. The method of claim 3, wherein in step 1 and step 2, the total molar concentration of Ni, co and Al metal ions in the Ni, co and Al mixed salt solution is 1.0 mol/L-2.5 mol/L, and the total molar concentration of Ni, co and Al metal ions in the Ni, co mixed salt solution is 1.0 mol/L-2.5 mol/L.
6. The method for preparing nickel cobalt aluminum hydroxide with narrow distribution and large particle size according to claim 3, wherein the molar concentration of the prepared sodium hydroxide solution in step 3 is 4.0mol/L to 11.0mol/L.
7. The method for preparing nickel cobalt aluminum hydroxide with narrow distribution and large particle size according to claim 3, wherein the molar concentration of Al in the prepared aluminum-alkali mixed solution in the step 4 is 0.1 mol/L-0.8 mol/L.
8. The method for preparing nickel cobalt aluminum hydroxide with narrow distribution and large particle size according to claim 3, wherein the concentration of the prepared ammonia water in the step 5 is 6.0mol/L to 12.0mol/L.
9. The method for preparing the narrow-distribution large-particle-size nickel-cobalt-aluminum hydroxide according to claim 3, wherein in the step 6, the ammonia concentration of the prepared ammonia-ammonium solution is 2.0mol/L to 15.0mol/L, and the mass ratio of the ammonia water to the ammonium salt is 10.
10. The method for preparing the nickel-cobalt-aluminum hydroxide with narrow distribution and large particle size according to claim 3, wherein in the step 8, the pH value of the base solution is 10.8-11.4, and the ammonia concentration is 2.0 g/L-10.0 g/L.
11. The method for preparing the nickel-cobalt-aluminum hydroxide with the narrow distribution and the large particle size according to claim 3, wherein in the step 9, the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is controlled to be 10.8-11.4, and the ammonia concentration is controlled to be 2.0-10.0 g/L.
12. The method for preparing the nickel-cobalt-aluminum hydroxide with the narrow distribution and the large particle size according to claim 3, wherein in the step 10, the reaction temperature in the kettle is controlled to be 45-65 ℃, the pH value is controlled to be 10.8-11.4, and the ammonia concentration is controlled to be 8.0-14.0 g/L.
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