CN111717939A - 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
- Publication number
- CN111717939A CN111717939A CN202010571905.XA CN202010571905A CN111717939A CN 111717939 A CN111717939 A CN 111717939A CN 202010571905 A CN202010571905 A CN 202010571905A CN 111717939 A CN111717939 A CN 111717939A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- aluminum
- solution
- aluminum hydroxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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 m2The specific surface area of the whole of the precursor secondary spherical particles is 7-15 m2(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; on one hand, the preparation method of the nickel-cobalt-aluminum hydroxide with narrow distribution and large particle size overcomes the defect that the precursor synthesized by a solid phase method cannot reach the atomic levelOn the other hand, the method also overcomes the aluminum hydroxide flocculent precipitate generated in the synthesis process of the conventional liquid phase method, and obtains 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 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 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 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 the ammonia water,therefore, when the 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 extremely easy to form, and not only a uniform single layered structure is difficult to form with nickel and cobalt precipitates, but also a spherical large-particle precipitate is difficult to form, so that the performance index of the NCA material obtained 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 a 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, it causes 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 a narrow distribution and a 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 m2The specific surface area of the whole of the precursor secondary spherical particles is 7-15 m2(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, K90= (D90-D10)/D50 is not more than 0.90, 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, and the inner layer of the precursor is a loose knot with larger specific surface areaWhen the cathode 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 cathode 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 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 m2A specific surface area of 7 to 15m in the whole particle2(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.
The D50 of the inner layer of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide 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 the D50 of the materials in the reaction kettle is detected to reach 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.
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 2.0-15.0 mol/L, and the mass ratio of the ammonia water to the ammonium salt is 10: 0.1-3.0.
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 preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 9, the reaction temperature in a 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 preparation method of the narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide, in the step 10, the reaction temperature in a kettle is controlled to be 45-65 ℃, the pH value is 10.8-11.4, and the ammonia concentration is 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 and specific surface area, less impurities and a better layered structure, 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 m2The specific surface area of the whole of the precursor secondary spherical particles is 7-15 m2(ii)/g; inner and outer layer of grainsThe particles contain three elements of nickel, cobalt and aluminum, wherein the nickel accounts for 85-98% of the total molar content of the metal; 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 9.0-20.0 μm, 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 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 a narrowly-distributed large-particle-size nickel-cobalt-aluminum hydroxide overcomes the defects that a precursor synthesized by a solid phase method cannot achieve uniformity of an atomic level, overcomes aluminum hydroxide flocculent precipitates generated in a synthesis process of a conventional liquid phase method to obtain a precursor with a double-layer structure with a loose inner layer and a tight outer layer, has the characteristics of good sphericity, stable structure and high consistency, changes the principle of nucleation and crystallization growth by regulating and controlling the addition mode of an aluminum source, forms an inner core with a large specific surface area inside particles and forms a shell with a small specific surface area outside the particles, promotes lithium sources to be rapidly diffused into the particles in a sintering process, and improves the uniformity of materials. 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 a narrow distribution 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 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 m2A specific surface area of 7 to 15m in the whole particle2(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 88% -90%; the particles have the characteristic of narrow distribution, wherein 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, preparing a nickel-cobalt-aluminum mixed salt solution with the total metal ion concentration of 2mol/L by using nickel, cobalt and aluminum soluble salts as raw materials and pure water according to the molar ratio of nickel, cobalt and aluminum elements in the inner layer of the required nickel-cobalt-aluminum hydroxide, namely 89:9: 2;
step 2, 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 according to the molar ratio of nickel to cobalt in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 89: 9;
step 3, preparing a sodium hydroxide solution with the concentration of 10.0 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 0.2 mol/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 10:2 to prepare an ammonia-ammonium solution, wherein the ammonia concentration of the ammonia-ammonium solution is 10.0 mol/L;
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 7.0 g/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 7.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 9.0 mu m, stopping feeding;
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 9.0 g/L;
step 11, stopping all feeding materials when the D50 of the materials in the reaction kettle is detected to reach 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 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 m2A specific surface area of 7 to 15m in the whole particle2(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, preparing a nickel-cobalt-aluminum mixed salt solution with the total metal ion concentration of 1.8mol/L by using nickel, cobalt and aluminum soluble salts as raw materials and pure water according to the molar ratio of nickel, cobalt and aluminum elements in the inner layer of the required nickel-cobalt-aluminum hydroxide, namely 92:7: 1;
step 2, preparing a nickel-cobalt mixed salt solution with the total metal ion concentration of 1.8mol/L by using nickel and cobalt soluble salts as raw materials and pure water according to the molar ratio of nickel to cobalt in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 92: 7;
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 0.4 mol/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 10:2 to prepare an ammonia-ammonium solution, wherein the ammonia concentration of the ammonia-ammonium solution is 10.0 mol/L;
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 5.0 g/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 5.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 7.0 mu m, stopping feeding;
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 at 50 ℃, the pH value is 11.3, and the ammonia concentration is 12.0 g/L;
step 11, stopping all feeding materials when the D50 of the materials in the reaction kettle is detected to reach 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 m2A specific surface area of 7 to 15m in the whole particle2(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 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, preparing a nickel-cobalt-aluminum mixed salt solution with the total metal ion concentration of 1.5mol/L by using nickel, cobalt and aluminum soluble salts as raw materials and pure water according to the molar ratio of nickel, cobalt and aluminum elements in the inner layer of the required nickel-cobalt-aluminum hydroxide, namely 95:3: 2;
step 2, according to the molar ratio of nickel and cobalt elements in the outer layer of the required nickel-cobalt-aluminum hydroxide, namely 95:3, preparing a nickel-cobalt mixed salt solution with the total metal ion concentration of 1.5mol/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 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 0.5 mol/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 10:2 to prepare an ammonia-ammonium solution, wherein the ammonia concentration of the ammonia-ammonium solution is 10.0 mol/L;
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 9.0 g/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 9.0 g/L; when the D50 of the material in the reaction kettle is detected to reach 14.0 mu m, stopping feeding;
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 12.0 g/L;
step 11, stopping all feeding materials when the D50 of the materials in the reaction kettle is detected to reach 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 large-particle-size nickel-cobalt-aluminum hydroxide is characterized in that 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 m2A specific surface area of 7 to 15m in the whole particle2(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 inner layer of particles has a D50 of 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 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 the D50 of the materials in the reaction kettle is detected to reach 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 the nickel-cobalt-aluminum hydroxide with the narrow distribution and the large particle size according to claim 3, wherein in the step 1 and the 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 the step 3 is 4.0mol/L to 11.0 mol/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 12.0 mol/L.
9. The method for preparing the narrowly distributed 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 2.0 mol/L-15.0 mol/L, and the mass ratio of the ammonia water to the ammonium salt is 10: 0.1-3.0.
10. 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 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 10.8-11.4, and the ammonia concentration is 8.0-14.0 g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010571905.XA CN111717939B (en) | 2020-06-22 | 2020-06-22 | Narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010571905.XA CN111717939B (en) | 2020-06-22 | 2020-06-22 | Narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111717939A true CN111717939A (en) | 2020-09-29 |
| CN111717939B CN111717939B (en) | 2022-10-14 |
Family
ID=72569784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010571905.XA Active CN111717939B (en) | 2020-06-22 | 2020-06-22 | Narrowly distributed large-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111717939B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928250A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-cobalt-manganese ternary material and precursor thereof, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN103094546A (en) * | 2013-01-25 | 2013-05-08 | 湖南邦普循环科技有限公司 | Method for preparing nickel-cobalt lithium aluminate as anode material of lithium ion battery |
| CN103296263A (en) * | 2012-12-28 | 2013-09-11 | 深圳市天骄科技开发有限公司 | Preparation method of lithium-ion battery positive electrode material spherical nickel-cobalt-lithium aluminate |
| CN105390691A (en) * | 2015-10-23 | 2016-03-09 | 赣州市芯隆新能源材料有限公司 | Method for preparing spherical nickel cobalt lithium manganate by liquid phase template method |
| CN110224123A (en) * | 2019-06-13 | 2019-09-10 | 广东邦普循环科技有限公司 | A kind of high voltage lithium cobalt oxide anode and its preparation method and application |
| CN110372020A (en) * | 2019-08-29 | 2019-10-25 | 山东省化工研究院 | A kind of preparation method of high-efficiency oxy-hydrogen aluminium crystal seed |
| CN111017969A (en) * | 2019-12-20 | 2020-04-17 | 湖南诺兰蒂尔环保科技有限公司 | Crystallization auxiliary agent for decomposing sodium aluminate seed crystal and preparation method of aluminum hydroxide |
-
2020
- 2020-06-22 CN CN202010571905.XA patent/CN111717939B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101447566A (en) * | 2008-12-29 | 2009-06-03 | 清华大学深圳研究生院 | Li-ion battery positive electrode material with layered-spinel symbiotic structure and preparation method |
| CN103296263A (en) * | 2012-12-28 | 2013-09-11 | 深圳市天骄科技开发有限公司 | Preparation method of lithium-ion battery positive electrode material spherical nickel-cobalt-lithium aluminate |
| CN103094546A (en) * | 2013-01-25 | 2013-05-08 | 湖南邦普循环科技有限公司 | Method for preparing nickel-cobalt lithium aluminate as anode material of lithium ion battery |
| CN105390691A (en) * | 2015-10-23 | 2016-03-09 | 赣州市芯隆新能源材料有限公司 | Method for preparing spherical nickel cobalt lithium manganate by liquid phase template method |
| CN110224123A (en) * | 2019-06-13 | 2019-09-10 | 广东邦普循环科技有限公司 | A kind of high voltage lithium cobalt oxide anode and its preparation method and application |
| CN110372020A (en) * | 2019-08-29 | 2019-10-25 | 山东省化工研究院 | A kind of preparation method of high-efficiency oxy-hydrogen aluminium crystal seed |
| CN111017969A (en) * | 2019-12-20 | 2020-04-17 | 湖南诺兰蒂尔环保科技有限公司 | Crystallization auxiliary agent for decomposing sodium aluminate seed crystal and preparation method of aluminum hydroxide |
Non-Patent Citations (2)
| Title |
|---|
| 厉衡隆，顾松青主编: "《铝冶炼生产技术手册 上》", 31 July 2011, 冶金工业出版社 * |
| 邱天等: ""镍钴铝酸锂前驱体Ni0.80Co0.15Al0.05(OH)2洗涤降硫工艺"", 《电源技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112928250A (en) * | 2021-01-22 | 2021-06-08 | 厦门厦钨新能源材料股份有限公司 | Nickel-cobalt-manganese ternary material and precursor thereof, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111717939B (en) | 2022-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721109B (en) | Nickel-cobalt-manganese ternary positive electrode material precursor for lithium battery, preparation method of precursor and prepared positive electrode material | |
| CN115000399B (en) | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN111422926B (en) | Core-shell structure Al/La co-doped high-nickel ternary precursor and preparation method thereof, and anode material | |
| CN109455772B (en) | Modified precursor and anode material for lithium ion battery and preparation methods of precursor and anode material | |
| CN109742337B (en) | Ternary cathode material precursor and method for regulating crystal face growth of ternary cathode material precursor | |
| CN112086616B (en) | Preparation method of large (010) crystal face nickel-cobalt-manganese/aluminum layered positive electrode material | |
| CN111717938B (en) | Narrowly distributed small-particle-size nickel-cobalt-aluminum hydroxide and preparation method thereof | |
| CN106159254B (en) | Nano-sheet ternary or rich lithium manganese base solid solution positive electrode material precursor preparation method | |
| CN111816877A (en) | High-nickel cobalt-free quaternary anode material and preparation method thereof | |
| CN108767216B (en) | Lithium ion battery anode material with variable slope and full concentration gradient and synthesis method thereof | |
| CN113321245B (en) | Nickel-cobalt-manganese hydroxide and preparation method thereof | |
| CN111600010B (en) | Preparation method of single crystal large particles of ternary material | |
| WO2022188480A1 (en) | Precursor of composite positive electrode material for lithium battery and preparation method for composite positive electrode material | |
| CN111018006A (en) | Preparation method of core-shell structure high-nickel ternary cathode material | |
| CN111453778A (en) | Tungsten-doped ternary precursor and preparation method thereof | |
| CN111029561A (en) | Ternary lithium battery positive electrode material precursor and preparation method thereof, ternary lithium battery positive electrode material and preparation method and application thereof | |
| CN108428888B (en) | Spherical surface compact nickel-cobalt-aluminum ternary material, precursor thereof, preparation method and application thereof | |
| JP2024507080A (en) | Sodium ion battery positive electrode active material and its manufacturing method and use | |
| CN113772748B (en) | Preparation method of lithium ion battery anode material | |
| CN108264096B (en) | Preparation method of high-density small-particle nickel-cobalt-manganese hydroxide | |
| CN113603153B (en) | Tungsten doped high nickel cobalt-free precursor and preparation method thereof | |
| CN108862406A (en) | A kind of carbonate precursor and its preparation method and application | |
| CN108807967B (en) | Preparation method of nickel-cobalt-aluminum ternary cathode material | |
| CN115231627B (en) | Preparation method of large monocrystal nickel-cobalt-manganese positive electrode material | |
| CN107732232A (en) | A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220328 Address after: 324000 No. 1, building 9, No. 18, Nianxin Road, high tech Industrial Park, Kecheng District, Quzhou City, Zhejiang Province Applicant after: HUAYOU NEW ENERGY TECHNOLOGY (QUZHOU) Co.,Ltd. Applicant after: ZHEJIANG HUAYOU COBALT Co.,Ltd. Address before: 324000 No.1, building 9, No.18, Nianxin Road, Quzhou City, Zhejiang Province Applicant before: HUAYOU NEW ENERGY TECHNOLOGY (QUZHOU) Co.,Ltd. Applicant before: ZHEJIANG HUAYOU COBALT Co.,Ltd. Applicant before: QUZHOU HUAHAI NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |