CN113697870B - Nickel hydroxide cobalt manganese precursor and preparation method thereof - Google Patents
Nickel hydroxide cobalt manganese precursor and preparation method thereof Download PDFInfo
- Publication number
- CN113697870B CN113697870B CN202111258717.2A CN202111258717A CN113697870B CN 113697870 B CN113697870 B CN 113697870B CN 202111258717 A CN202111258717 A CN 202111258717A CN 113697870 B CN113697870 B CN 113697870B
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- solution
- precursor
- manganese
- 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.)
- Active
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2006/11—Powder tap density
-
- 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
- H01M2004/026—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
Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly discloses a nickel hydroxide cobalt manganese precursor and a preparation method thereof. The precursor is a dual-core twin structure and is provided with channels which are arranged from the center to the outside in an emitting shape. The preparation of the precursor comprises the following steps: adding pure water into the reaction kettle, protecting with nitrogen, and pumping nickel-cobalt-manganese mixed metal salt solution containing ammonium salt solution; after ammonia water is added into the reaction kettle, when the phenomenon that floccules are not generated is observed, pumping the nickel-cobalt-manganese mixed metal salt solution, the complexing agent solution and the precipitator solution, and further increasing the flow of the nickel-cobalt-manganese mixed metal salt solution when the reaction slurry reaches a target value. The precursor prepared by the invention is beneficial to lithium ion diffusion, and has good consistency and excellent performance; the preparation method has stable process and mass production conditions.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a nickel-cobalt-manganese hydroxide precursor and a preparation method thereof.
Background
With the breakthrough of new technology, the battery field has been developed greatly in recent years, and lithium ion batteries are widely used in the fields of 3C digital products and electric vehicles as a material with mature technology. The positive electrode material is one of the key materials of the lithium ion battery, and as the performance requirements of the lithium ion battery are higher and higher, the positive electrode material and the precursor thereof also face the challenges of higher energy density, faster charge and discharge efficiency and longer service life. Research shows that the above challenges require that lithium ion channels in the positive electrode material are more unobstructed and less irreversible reactions occur in the charge and discharge processes. The physical property index of the precursor directly determines the performance of the anode material, and further reflects the performance of the lithium ion battery. In the sintering process of the ternary anode material, the polycrystalline large-particle precursor is tightly packed inside due to the close packing of primary particles, so that the Li ion embedding speed is low, irregular particles can cause uneven lithium melting inside and outside the particles, and finally, the residual lithium of the anode material is higher and the capacity is lower. The preparation of the precursor with a specific morphology is particularly important for improving the lithium ion deintercalation rate of the anode material and increasing the lithium ion channels. The preparation method of the nickel-cobalt-manganese hydroxide precursor is researched a lot in the industry, the size of secondary particles and the morphology of primary particles of the precursor are related, but the internal morphology and the binuclear structure are not fully researched. For example: chinese patent publication No. CN113258062A discloses a precursor of a radial truncated cone-like structure, which has an irregular shape, and lithium ions cannot enter the interior of the precursor uniformly during the lithium mixing and sintering process. The precursor disclosed in chinese patent publication No. CN107342417B has a mononuclear structure inside, and does not provide more radiation channels than binuclear sites.
Disclosure of Invention
Aiming at the problems in the prior art, one of the purposes of the invention is to provide a precursor with a specific morphology, and the obtained positive electrode material after mixed lithium calcination has more lithium ion channels and higher lithium ion de-intercalation rate; the other purpose of the invention is to provide a preparation method of the precursor with the specific morphology.
In order to achieve the above object, the present invention provides the following technical solutions.
A precursor of nickel cobalt manganese hydroxide with a molecular formula of NixCoyMn1-x-y(OH)2Wherein x + y is less than or equal to 1; the secondary particles of the precursor are spheres of 15-25 mu m, and the center of each sphere is a binuclear twin structure; the ball body is provided with channels which are arranged in an emitting shape from the center to the outside. The gap between adjacent channels is 0.1-2 μm. The channel is cylindrical or trumpet-shaped and has an included angle of 0-30 degrees.
Further, the aspect ratio of the primary particles of the precursor is 1 to 6, and the radial distance distribution of the secondary particles is 0.4 to 1.0. The specific calculation method of the radial distance is (D90-D10)/D50.
Further, the specific surface area of the precursor is 2-18cm2(ii) g, tap density of 0.7-2.5g/cm3，D10>10μm，D90<35μm。
The precursor has a dual-core structure, and has emissive channels inside, and the number of channels inside from inside to outside is increased, so that more sites for contacting lithium salt can be provided.
Based on the same inventive concept, the invention provides a preparation method of the nickel hydroxide cobalt manganese precursor, which comprises the following steps:
(6) preparing a nickel-cobalt-manganese mixed salt solution, a precipitator solution and a complexing agent solution;
(7) adding ammonium salt into the nickel-cobalt-manganese mixed salt solution to obtain a mixed solution A;
(8) adding pure water into a reaction kettle, introducing nitrogen, then adding the mixed solution A, controlling the reaction temperature to be 50-85 ℃, stirring, then adding ammonia water, continuously observing the reaction system, when the floccule in the reaction system is not increased any more, adding a nickel-cobalt-manganese mixed salt solution, a complexing agent solution and a precipitator solution in parallel, keeping the pH value of the reaction system to be 9-11 and the alkalinity to be 3-20g/L until the granularity of the reaction slurry reaches a target value;
(9) further increasing the flow of the nickel-cobalt-manganese mixed salt solution until the granularity of the reaction slurry reaches a preset value;
(10) and after solid-liquid separation of the reaction slurry, aging, washing and drying the solid phase to obtain the nickel-cobalt-manganese hydroxide precursor.
Further, in the preparation method, the total concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 2-2.4 mol/L; the concentration of the precipitant solution is 2-10 mol/L; the concentration of the complexing agent solution is 2-13 mol/L.
Preferably, the precipitant is NaOH, and the complexing agent is ammonia water.
Further, in the above preparation method, the ammonium salt is selected from one or more of ammonium bicarbonate, ammonium carbonate, ammonium sulfide, ammonium sulfate, ammonium nitrate and ammonium chloride.
Further, in the above production method, the concentration of the ammonium salt in the mixed solution A is 0.0001 to 1 g/ml.
Further, in the preparation method, the adding volume of the pure water in the step (3) is 1/3-2/3 of the total volume of the reaction kettle; the adding volume of the mixed solution A is 5-20% of the total volume of the reaction kettle; the concentration of the ammonia water is 25wt% -28wt%, and the adding amount of the ammonia water is the same as that of the mixed solution A.
Further, in the preparation method, the flow rate of the nickel-cobalt-manganese mixed salt solution in the step (3) is 30-200 ml/min.
Further, in the preparation method, the flow rate of the nickel-cobalt-manganese mixed salt solution in the step (4) is 1.5 to 3 times of the flow rate of the nickel-cobalt-manganese mixed salt solution in the step (3).
Further, in the above preparation method, the target value in the step (3) is 3 to 10 μm, and the preset value in the step (4) is 15 to 25 μm.
Further, in the above production method, the floc is observed by a microscope.
Further, in the above preparation method, the aging in the step (5) uses a 5% diluted alkali solution; the washing is carried out using pure water until the pH of the wash water is < 8.2; the drying temperature is 100-150 ℃.
The invention also provides a positive electrode material which is obtained by calcining the precursor mixed lithium.
Compared with the prior art, the precursor provided by the invention has a binuclear twin structure and channels, and the number of the channels inside the precursor from inside to outside is increased, so that more contact sites with lithium salt can be provided, the lithium ion deintercalation rate of the anode material is increased, and the performance of the anode material is improved.
Drawings
FIGS. 1 to 3 are sectional electron micrographs of the precursor prepared in example 1.
FIG. 4 is a graph showing the particle size distribution of the precursor prepared in example 1.
FIG. 5 is a sectional electron micrograph of the precursor prepared in example 2.
FIG. 6 is a graph showing the particle size distribution of the precursor prepared in example 2.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description of the invention taken in conjunction with the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory of the invention and are not restrictive thereof. Additionally, the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Example 1
The embodiment comprises the following steps:
(1) preparing a nickel-cobalt-manganese sulfate solution with the total concentration of nickel-cobalt-manganese metal ions being 2mol/L, wherein the molar ratio of Ni to Co to Mn is 0.5: 0.2: 0.3. and adding 200g of ammonium bicarbonate into 5L of nickel-cobalt-manganese sulfate solution, and uniformly mixing to obtain a mixed solution A.
5mol/L ammonia water solution and 3mol/L sodium hydroxide solution are prepared.
(2) Adding pure water into the reaction kettle, wherein the volume of the pure water is 1/3 of the total volume of the reaction kettle, introducing nitrogen, starting stirring at the rotating speed of 540rpm, and setting the reaction temperature to be 55 ℃.
(3) Pumping the mixed solution A accounting for 5 percent of the total volume of the reaction kettle into the reaction kettle, fully and uniformly stirring, adding ammonia water with the same volume, and continuously observing under a microscope to obtain the floccule in a semi-transparent flaky frog egg shape.
(4) And (3) adding a nickel-cobalt-manganese sulfate solution, an ammonia water solution and a sodium hydroxide solution in parallel when the floccule is not increased any more, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 100ml/min, the pH of the reaction system is controlled to be about 9.7, and the alkalinity is adjusted to be 3 g/L.
(5) After the median particle size of the reaction slurry grows to 9 microns, doubling the flow of the nickel-cobalt-manganese sulfate solution, adjusting the rotating speed to 486rpm, starting a concentrator when the volume of the solution in the reaction kettle is close to the high level, continuously discharging the supernatant, and stopping the reaction when the median particle size of the reaction slurry is 15.57 microns.
(6) And (3) carrying out solid-liquid separation on the reaction slurry, and sequentially carrying out 5% diluted alkali aging, pure water washing, drying at 100 ℃ for 12 hours and 200-mesh screen sieving on the solid phase to finally obtain the precursor.
Fig. 1-3 are sectional electron micrographs of the precursor prepared in this example, from which it is apparent that the precursor has a dual-core structure and has channels emitting from the inside to the outside with a certain angle. Fig. 4 shows the results of the particle size test of the precursor, and the pitch of the precursor was 0.621.
Example 2
The embodiment comprises the following steps:
(1) preparing a nickel-cobalt-manganese sulfate solution with the total concentration of nickel-cobalt-manganese metal ions of 2.2mol/L, wherein the molar ratio of Ni to Co to Mn is 0.8: 0.1: 0.1, taking 10L of nickel cobalt manganese sulfate solution, adding 600g of ammonium sulfide, and uniformly mixing to obtain a mixed solution A.
5mol/L ammonia water solution and 3mol/L sodium hydroxide solution are prepared.
(2) Adding pure water into the reaction kettle, wherein the volume of the pure water is 2/3 of the total volume of the reaction kettle, introducing nitrogen, starting stirring at the rotating speed of 540rpm, and setting the reaction temperature to be 65 ℃.
(3) Pumping the mixed solution A accounting for 10 percent of the total volume of the reaction kettle into the reaction kettle, fully and uniformly stirring, adding the ammonia water solution with the same volume, and continuously observing under a microscope.
(4) And (3) adding a nickel-cobalt-manganese sulfate solution, an ammonia water solution and a sodium hydroxide solution in parallel when the floccule is not increased any more, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 120ml/min, the pH value of the reaction system is controlled to be about 11.5, and the alkalinity is adjusted to be 6 g/L.
(5) After the median particle size of the reaction slurry grows to 7 microns, doubling the flow of the nickel-cobalt-manganese sulfate, adjusting the rotating speed to 430rpm, starting a concentrator when the volume of the solution in the reaction kettle is close to the high level, continuously discharging the supernatant, and stopping the reaction when the median particle size of the reaction slurry is 18 microns.
(6) After solid-liquid separation of the reaction slurry, the solid phase is sequentially subjected to 5% diluted alkali aging, pure water washing, drying at 120 ℃ for 12 hours, and sieving by a 200-mesh sieve to obtain a precursor.
FIG. 5 is a sectional electron micrograph of the precursor prepared in this example. As is evident from the figure, the precursor has a dual-core structure and channels which are in an emission shape from inside to outside. Fig. 6 is a particle size distribution diagram of the prepared precursor, the precursor having a diameter distance of 0.634.
Example 3
The embodiment comprises the following steps:
(1) preparing a nickel-cobalt-manganese sulfate solution with the total metal ion concentration of nickel-cobalt-manganese being 2.2mol/L, wherein the molar ratio of Ni to Co to Mn is 0.8: 0.1: 0.1, adding 770g of ammonium sulfate, 1920g of ammonium nitrate and 200g of ammonium chloride into 10L of nickel-cobalt-manganese sulfate solution, and uniformly mixing to obtain a mixed solution A.
5mol/L ammonia water solution and 3mol/L sodium hydroxide solution are prepared.
(2) Adding pure water into the reaction kettle, wherein the volume of the pure water is 1/3 of the total volume of the reaction kettle, introducing nitrogen, starting stirring at the rotating speed of 540rpm, and setting the reaction temperature at 75 ℃.
(3) Pumping the mixed solution A accounting for 15 percent of the total volume of the reaction kettle into the reaction kettle, fully and uniformly stirring, adding an ammonia water solution with the same volume, and continuously observing under a microscope.
(4) And (3) adding a nickel-cobalt-manganese sulfate solution, an ammonia water solution and a sodium hydroxide solution in parallel when the floccule is not increased any more, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 120ml/min, the pH value of the reaction system is controlled to be about 11.5, and the alkalinity is adjusted to be 6 g/L.
(5) And after the median particle size of the reaction slurry grows to 7 microns, turning over the flow of the nickel-cobalt-manganese sulfate solution by 1.5 times, adjusting the rotating speed to 370rpm, starting a concentrator when the volume of the solution in the reaction kettle is close to the high level, continuously discharging the supernatant, and stopping the reaction when the median particle size of the reaction slurry reaches 20 microns.
(6) And after solid-liquid separation of the reaction slurry, carrying out 5% diluted alkali aging, pure water washing, drying at 120 ℃ for 12 hours and sieving by a 200-mesh sieve on the solid phase in sequence to obtain a precursor.
Example 4
The embodiment comprises the following steps:
(1) preparing a nickel-cobalt-manganese sulfate solution with the total metal ion concentration of nickel-cobalt-manganese being 2.2mol/L, wherein the molar ratio of Ni to Co to Mn is 0.95: 0.02: 0.03, taking 15L of nickel cobalt manganese sulfate solution, adding 600g of ammonium sulfide and 1920g of ammonium nitrate, and uniformly mixing to obtain a mixed solution A.
5mol/L ammonia water solution and 3mol/L sodium hydroxide solution are prepared.
(2) Adding pure water into the reaction kettle, wherein the volume of the pure water is 1/3 of the total volume of the reaction kettle, introducing nitrogen, starting stirring at the rotating speed of 540rpm, and setting the reaction temperature at 75 ℃.
(3) Pumping the mixed solution A accounting for 20 percent of the total volume of the reaction kettle into the reaction kettle, fully and uniformly stirring, adding an ammonia water solution with the same volume, and continuously observing under a microscope.
(4) And (3) adding a nickel-cobalt-manganese sulfate solution, an ammonia water solution and a sodium hydroxide solution in parallel when the floccule is not increased any more, wherein the flow rate of the nickel-cobalt-manganese sulfate solution is 120ml/min, the pH of the reaction system is controlled to be about 11.8, and the alkalinity is adjusted to be 15 g/L.
(5) After the median particle size of the reaction slurry grows to 8 microns, doubling the flow of the nickel-cobalt-manganese sulfate, adjusting the rotating speed to 320rpm, starting a concentrator when the volume of the solution in the reaction kettle is close to the high level, continuously discharging the supernatant, and stopping the reaction when the median particle size of the reaction slurry reaches 20 microns.
(6) After solid-liquid separation of the reaction slurry, the solid phase is sequentially subjected to 10% diluted alkali aging, pure water washing, drying at 120 ℃ for 12 hours, and sieving by a 200-mesh sieve to obtain a precursor.
The aspect ratios of the primary particles of the precursors prepared in examples 1 to 4 were further analyzed, and the results are shown in table 1.
Table 1 primary particle aspect ratio of precursors prepared in examples 1 to 4
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A precursor of nickel cobalt manganese hydroxide with a molecular formula of NixCoyMn1-x-y(OH)2Wherein x + y is less than or equal to 1; the method is characterized in that secondary particles of the precursor are spheres of 15-25 mu m, and the center of each sphere is a binuclear twin structure; channels which are arranged in an emitting shape are arranged outwards from the center of the sphere, and the gap between every two adjacent channels is 0.1-2 mu m; the channel is cylindrical or trumpet-shaped and has a diameter of 0-30%Angle of degree.
2. The nickel cobalt manganese hydroxide precursor according to claim 1, wherein the primary particles of said precursor have an aspect ratio of 1 to 6 and a radial distance distribution of secondary particles of 0.4 to 1.0.
3. The nickel cobalt manganese hydroxide precursor according to claim 1 or 2, wherein the specific surface area of the precursor is from 2 to 18cm2(ii) g, tap density of 0.7-2.5g/cm3，D10>10μm，D90<35μm。
4. A preparation method of a nickel-cobalt-manganese hydroxide precursor is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese mixed salt solution, a precipitator solution and a complexing agent solution; the total concentration of metal ions in the nickel-cobalt-manganese mixed salt solution is 2-2.4 mol/L; the concentration of the precipitant solution is 2-10 mol/L; the concentration of the complexing agent solution is 2-13 mol/L;
(2) adding ammonium salt into the nickel-cobalt-manganese mixed salt solution to obtain a mixed solution A; the concentration of ammonium salt in the mixed solution A is 0.0001-1 g/ml;
(3) adding pure water into a reaction kettle, introducing nitrogen, and then adding a mixed solution A, wherein the adding volume of the mixed solution A is 5-20% of the total volume of the reaction kettle; controlling the reaction temperature to be 50-85 ℃, stirring, and then adding ammonia water, wherein the concentration of the ammonia water is 25-28 wt%, and the adding amount of the ammonia water is the same as that of the mixed solution A; continuously observing the reaction system, when the floccule in the reaction system is not increased any more, adding a nickel-cobalt-manganese mixed salt solution, a complexing agent solution and a precipitator solution in a concurrent flow manner, and keeping the pH value of the reaction system to be 9-11 and the alkalinity to be 3-20g/L until the granularity of the reaction slurry reaches a target value; the flow rate of the nickel-cobalt-manganese mixed salt solution is 30-200 ml/min;
(4) further increasing the flow of the nickel-cobalt-manganese mixed salt solution to be 1.5-3 times of the flow of the nickel-cobalt-manganese mixed salt solution in the step (3) until the granularity of the reaction slurry reaches a preset value;
(5) and after solid-liquid separation of the reaction slurry, aging, washing and drying the solid phase to obtain the nickel-cobalt-manganese hydroxide precursor.
5. The method according to claim 4, wherein the ammonium salt is selected from one or more of ammonium bicarbonate, ammonium carbonate, ammonium sulfide, ammonium sulfate, ammonium nitrate and ammonium chloride.
6. The method according to claim 4, wherein the pure water is added in the step (3) in an amount of 1/3 to 2/3 parts by volume based on the total volume of the reaction vessel.
7. The method according to claim 4, wherein the target value in step (3) is 3 to 10 μm, and the predetermined value in step (4) is 15 to 25 μm.
8. A positive electrode material obtained by calcining the precursor lithium-mixed according to any one of claims 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111258717.2A CN113697870B (en) | 2021-10-28 | 2021-10-28 | Nickel hydroxide cobalt manganese precursor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111258717.2A CN113697870B (en) | 2021-10-28 | 2021-10-28 | Nickel hydroxide cobalt manganese precursor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113697870A CN113697870A (en) | 2021-11-26 |
| CN113697870B true CN113697870B (en) | 2022-02-08 |
Family
ID=78647524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111258717.2A Active CN113697870B (en) | 2021-10-28 | 2021-10-28 | Nickel hydroxide cobalt manganese precursor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113697870B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024088271A1 (en) | 2022-10-26 | 2024-05-02 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method for precursor and positive electrode material |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114031127B (en) * | 2021-12-20 | 2023-10-24 | 金驰能源材料有限公司 | Mg-Ti co-doped high-nickel cobalt-free precursor and preparation method thereof |
| CN114956201A (en) * | 2022-04-24 | 2022-08-30 | 南通金通储能动力新材料有限公司 | Large-particle ternary precursor and preparation method thereof |
| CN115924990B (en) * | 2022-11-30 | 2024-04-26 | 湖南中伟新能源科技有限公司 | Polynuclear precursor of sodium ion battery material, preparation method of polynuclear precursor, sodium ion battery positive electrode material, sodium ion battery and electric equipment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107342417A (en) * | 2016-12-28 | 2017-11-10 | 杉杉能源（宁夏）有限公司 | A kind of high ni-type precursor of nickel-cobalt-lithium-manganese-oxide with specific morphology and preparation method thereof |
| EP3281915A1 (en) * | 2016-08-10 | 2018-02-14 | Umicore | Precursors for lithium transition metal oxide cathode materials for rechargeable batteries |
| CN108417829A (en) * | 2018-03-13 | 2018-08-17 | 成都新柯力化工科技有限公司 | A kind of method that stabilization prepares the nickelic lithium battery tertiary material of monocrystalline |
-
2021
- 2021-10-28 CN CN202111258717.2A patent/CN113697870B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3281915A1 (en) * | 2016-08-10 | 2018-02-14 | Umicore | Precursors for lithium transition metal oxide cathode materials for rechargeable batteries |
| CN107342417A (en) * | 2016-12-28 | 2017-11-10 | 杉杉能源（宁夏）有限公司 | A kind of high ni-type precursor of nickel-cobalt-lithium-manganese-oxide with specific morphology and preparation method thereof |
| CN108417829A (en) * | 2018-03-13 | 2018-08-17 | 成都新柯力化工科技有限公司 | A kind of method that stabilization prepares the nickelic lithium battery tertiary material of monocrystalline |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024088271A1 (en) | 2022-10-26 | 2024-05-02 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method for precursor and positive electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113697870A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113697870B (en) | Nickel hydroxide cobalt manganese precursor and preparation method thereof | |
| CN109817970B (en) | Single crystal sodium ion battery electrode material and preparation method thereof | |
| CN111900401B (en) | Method for coating positive electrode material of lithium battery by using tungsten oxide and nitrogen-doped carbon composite | |
| CN112758991B (en) | Preparation method of core-shell structure ternary cathode material precursor | |
| CN109461891B (en) | High-voltage lithium cobalt oxide cathode material and preparation method thereof | |
| CN109786721B (en) | Positive electrode material, and preparation method and application thereof | |
| CN109411718B (en) | Preparation method of doping modified ternary cathode material | |
| CN112018341A (en) | High-capacity high-nickel cathode material and preparation method thereof | |
| CN111293305B (en) | Hexagonal flaky nickel cobalt lithium manganate precursor and preparation method thereof | |
| WO2022188480A1 (en) | Precursor of composite positive electrode material for lithium battery and preparation method for composite positive electrode material | |
| 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 | |
| CN114243014A (en) | Single crystal ternary cathode material and preparation method and application thereof | |
| CN114649525B (en) | Lithium-rich manganese-based@ternary composite precursor, positive electrode material and preparation method of positive electrode material | |
| CN113233519B (en) | Precursor of magnesium, antimony phosphate, aluminum and lithium phosphate co-modified high-nickel cobalt-free positive electrode material, preparation method of precursor and positive electrode material | |
| CN113880148B (en) | Ternary precursor and preparation method and application thereof | |
| CN111009645A (en) | graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material | |
| CN111592053A (en) | Nickel-based layered lithium ion battery positive electrode material and preparation method and application thereof | |
| CN110282665B (en) | Lithium battery positive electrode material precursor with mesoscopic structure and preparation method thereof | |
| CN115231627A (en) | Preparation method of large single crystal nickel-cobalt-manganese cathode material | |
| CN104078670A (en) | Composite lithium battery positive electrode material and preparation method thereof | |
| CN114031127B (en) | Mg-Ti co-doped high-nickel cobalt-free precursor and preparation method thereof | |
| CN114349069B (en) | High-nickel ternary positive electrode material precursor and preparation method thereof | |
| CN114220968A (en) | Coated LiMn0.5Fe0.5PO4Lithium ion battery anode material and preparation method thereof | |
| CN111994965B (en) | Preparation method of precursor of LTH-structure ternary cathode material | |
| CN110957488A (en) | Preparation method of peanut-like nickel cobalt lithium manganate positive electrode 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |