CN114530592B - Ternary cathode material and preparation method thereof - Google Patents

Ternary cathode material and preparation method thereof Download PDF

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CN114530592B
CN114530592B CN202210432766.1A CN202210432766A CN114530592B CN 114530592 B CN114530592 B CN 114530592B CN 202210432766 A CN202210432766 A CN 202210432766A CN 114530592 B CN114530592 B CN 114530592B
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precursor
ternary
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cathode material
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CN114530592A (en
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范未峰
张珏
雷英
王政强
张郑
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Yibin Libao New Materials Co Ltd
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • 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
    • 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 relates to the technical field of lithium battery materials, and discloses a ternary cathode material and a preparation method thereof. The preparation method comprises the following steps: mixing an alkaline solution with the concentration of more than or equal to 10mol/L and a precursor metal salt solution with the concentration of more than or equal to 2mol/L according to the molar ratio of hydroxyl in the solution to metal ions in the precursor metal salt of more than or equal to 2, carrying out mixing reaction for 0.1-60 min, and removing water from the obtained precipitate after the reaction is finished to obtain ternary precursor nano powder; mixing lithium hydroxide and ternary precursor nano powder for spheroidization, and loading the ternary precursor nano powder on lithium hydroxide particles to obtain a primary particle material; the primary particulate material is sintered. The method is simple and quick, has low cost, has no strict requirement on the particle size of the lithium hydroxide, and does not need to worry about the problem of precursor crushing; the nano-scale precursor has high reaction activity, and the lithium source and the precursor have good automatic dispersion effect. The ternary cathode material is prepared by the preparation method.

Description

Ternary cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a ternary cathode material and a preparation method thereof.
Background
The production scale of ternary cathode materials is increasingly expanding and is gradually developing on the market a pricing model in terms of "raw material cost + processing fees". For products composed of certain element proportions, the prices of metals such as nickel cobalt and lithium account for most of the production cost. Under the condition, the production process with high efficiency and low cost is developed through process innovation, and the method has direct significance for improving the market competitiveness of the ternary cathode material.
The existing ternary cathode material is generally prepared by coprecipitation of metals such as nickel, cobalt, manganese and the like to form a spherical precursor. In order to obtain a product which meets the size of a target product, multiple process conditions such as the addition speed, the pH value, the stirring speed, the liquid flow state, the longer recrystallization time and the like of various materials such as metal salts, sodium hydroxide, ammonia water and the like are strictly controlled to obtain a precursor which meets the index requirement, and the process cost accounts for about 50% of the cost in the whole production process of the ternary cathode material. In addition, when the spherical precursor is compounded with a lithium source, the requirement on the particle size of the used lithium hydroxide is high, while the common lithium hydroxide is generally in the form of particles with larger particle sizes, and needs to be refined before use, so that the refinement process can generate relatively unpleasant smell, and even if no unpleasant smell is generated, the production cost of the ternary cathode material can be increased by self-refining the refined lithium hydroxide or the ternary cathode material before preparation.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a ternary cathode material and a preparation method thereof, and aims to solve at least one problem in the background art.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a method for preparing a ternary cathode material, including:
mixing an alkaline solution with the concentration of more than or equal to 10mol/L of hydroxyl and a precursor metal salt solution with the concentration of more than or equal to 2mol/L according to the molar ratio of more than or equal to 2 of the hydroxyl in the alkaline solution to the metal ions in the precursor metal salt solution, carrying out mixing reaction for 0.1-60 min, and removing water from the obtained precipitate after the reaction is finished to obtain ternary precursor nano powder;
mixing lithium hydroxide and ternary precursor nano powder for spheroidization, and loading the ternary precursor nano powder on lithium hydroxide particles to obtain a primary particle material;
the primary particulate material is sintered.
In an alternative embodiment, the mixing reaction is maintained at a constant temperature.
In an optional embodiment, the temperature of the alkaline solution is 20 ℃ to 100 ℃, and the temperature of the precursor metal salt solution is 20 ℃ to 100 ℃.
In an alternative embodiment, the alkaline solution and the precursor metal salt solution are mixed at the same temperature.
In an optional embodiment, the mixing reaction temperature is 40-100 ℃, and the mixing reaction time is 0.1-15 min, preferably 0.1-5 min;
in an optional embodiment, the mixing reaction temperature is 40-100 ℃; preferably, the mixing reaction temperature is 60-80 ℃.
In an optional embodiment, the chemical formula of the obtained ternary precursor nano powder is NixCoyMn(1-x-y)(OH)2Wherein 0 is less than or equal to x<1，0≤y<1, and 0<x+y<1；
Preferably, the primary particle size of the ternary precursor nano powder is 20-200 nm.
In an alternative embodiment, the spheronization process is accomplished by mechanical fusion.
In an alternative embodiment, the mechanical fusion is performed on a fusion machine.
In an alternative embodiment, the fusion parameters are set as: the rotating speed is 700-900 rpm/min, and the fusion time is 10-50 min; the rotation speed is 900-1100 rpm/min, and the fusion time is 2-4 min.
In an alternative embodiment, the mixing reaction of the alkaline solution and the precursor metal salt solution is performed under a protective atmosphere, wherein the protective atmosphere is nitrogen or inert gas.
In an optional embodiment, lithium hydroxide particles and ternary precursor nano powder are mixed according to the Li/Me of 1-1.06.
In an optional embodiment, after the reaction of the alkaline solution and the precursor metal salt solution is finished, the obtained precipitate is washed at least once, and then moisture is removed to obtain the ternary precursor nano powder.
In an alternative embodiment, the step of removing water is to dry the precipitate in a vacuum environment at 80-180 ℃.
In an optional embodiment, the concentration of the alkaline solution is 10-30 mol/L.
In an optional embodiment, the concentration of the precursor metal salt solution is 2-3 mol/L.
In an alternative embodiment, the precursor metal salt solution is a sulphate, nitrate, acetate or hydrochloride solution, preferably a sulphate solution.
In alternative embodiments, the alkaline solution is an alkali metal solution or a carbonate solution; more preferably, the alkali metal solution is a solution in which the solute is at least one of sodium hydroxide and potassium hydroxide; more preferably, the carbonate solution is a solution having a solute of at least one of sodium carbonate and potassium carbonate.
In a second aspect, embodiments of the present invention provide a ternary cathode material, which is prepared by using the preparation method provided in any embodiment of the present invention.
The invention has the following beneficial effects:
the preparation method comprises the steps of reasonably designing the concentration of reaction raw materials and the reaction time to obtain nanoscale ternary precursor powder, compounding the nanoscale ternary precursor powder with a lithium source, loading the ternary precursor powder on the lithium source in the spheroidization process to obtain a primary particle material, and finally sintering to realize the preparation of the ternary cathode material. The whole process is simple and quick, and the cost is low; the particle size of the lithium hydroxide is not strictly required, the refined lithium hydroxide powder is not needed, and the problem of precursor crushing is not needed to be worried about; the nano-scale precursor has high reaction activity, and the lithium source and the precursor have good automatic dispersion effect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a SEM image of 10 ten thousand times of a sample prepared in example 1 of the present invention;
FIG. 2 is an SEM image of 20 ten thousand times of a sample prepared in example 1 of the present invention;
FIG. 3 is a 1 ten thousand SEM image of a sample prepared in comparative example 1 of the present invention;
FIG. 4 is a SEM image of 1 ten thousand times of a sample prepared in comparative example 2 of the present invention;
fig. 5 is an SEM image of the NCM523 positive electrode material prepared according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The ternary cathode material and the preparation method thereof provided by the present application are specifically described below.
The preparation method of the ternary cathode material provided by the embodiment of the application comprises the following steps:
mixing an alkaline solution with the concentration of more than or equal to 10mol/L of hydroxyl and a precursor metal salt solution with the concentration of more than or equal to 2mol/L according to the molar ratio of more than or equal to 2 of the hydroxyl in the alkaline solution to the metal ions in the precursor metal salt solution, carrying out mixing reaction for 2-60 min, and removing water from the obtained precipitate after the reaction is finished to obtain the ternary precursor nano-powder.
Mixing lithium hydroxide and ternary precursor nano powder, carrying out sphericizing treatment, and loading the ternary precursor nano powder on lithium hydroxide particles to obtain a primary particle material.
The primary particulate material is sintered.
The method comprises the steps of reacting a high-concentration alkaline solution with a high-concentration precursor metal salt solution, controlling the reaction time within 0.1-60 min, preventing product particles from growing up, obtaining nanoscale precursor powder with small particle size, compounding the nanoscale precursor powder with lithium hydroxide particles, loading the nanoscale precursor powder on the surfaces of the lithium hydroxide particles, and sintering to obtain the ternary cathode material. The method provided by the application has the following advantages: 1. ammonia water is not used in the preparation process of the ternary precursor, the reaction time is short, the complexity of the traditional precursor precipitation process is avoided, and the yield is improved; 2. the prepared nanoscale precursor powder is mixed with lithium hydroxide, and the nanoscale precursor powder is loaded on lithium hydroxide particles in the process of sphericizing, which is different from the existing preparation method that the lithium hydroxide is loaded on ternary precursor particles, so that the method provided by the application has no strict requirement on the granularity of the lithium hydroxide particles, the refined lithium hydroxide powder can be omitted, and the precursor is not required to be crushed; 3. the nano-scale precursor has high reaction activity, and the lithium source and the precursor have good automatic dispersion effect.
The preparation method specifically comprises the following steps:
s1 preparation of high-concentration alkaline solution
Preparing an alkaline solution with the concentration of more than or equal to 10mol/L by using a hydroxyl concentration meter, wherein the temperature is 20-100 ℃, the higher the temperature is, the higher the solubility is, and the highest possible value of the alkaline solution is the concentration value of the alkaline solution at the current temperature when the alkaline solution is saturated. Preferably, the concentration of the alkaline solution is 10-30 mol/L, such as 15 mol/L, 20mol/L, 25mol/L, 30mol/L, and the like.
Preferably, the alkaline solution is an alkali metal solution or a carbonate solution; more preferably, the alkali metal solution is a solution having a solute of at least one of sodium hydroxide and potassium hydroxide; more preferably, the carbonate solution is a solution having a solute of at least one of sodium carbonate and potassium carbonate.
The alkaline solution is selected from sodium hydroxide solution or sodium carbonate solution for production cost.
S2, preparing precursor metal salt solution
Using the conventional ternary precursor NixCoyMn(1-x-y)(OH)2Wherein 0 is less than or equal to x<1，0≤y<1, and 0<x+y<1 as the target product, dissolving at least one of nickel, cobalt and manganese in proper amount in acid solution, or taking proper amount of nickel salt and cobalt saltAt least one of salt and manganese salt is dissolved in the water solution to obtain a precursor metal salt solution with the concentration of more than or equal to 2 mol/L.
The temperature of the precursor metal salt solution is 20-100 ℃, the higher the temperature is, the higher the solubility is, and the larger the value of the highest concentration can be. Preferably, the concentration of the precursor salt solution is 2-3 mol/L, such as 2mol/L, 2.5mol/L, 3 mol/L.
Preferably, when the precursor metal salt solution contains manganese, the mixing reaction of the alkaline solution and the precursor metal salt solution is performed under a protective atmosphere to avoid oxidation of the manganese salt, and the protective gas is nitrogen or inert gas.
The precursor metal salt solution is a sulfate solution, a nitrate solution, an acetate solution or a hydrochloride solution. From the viewpoint of production cost, the precursor metal salt solution is preferably a sulfate salt solution.
S3, quick mixing reaction
And mixing the high-concentration alkaline solution and the precursor metal salt solution according to the molar ratio of hydroxyl in the solution to metal ions in the precursor metal salt being more than or equal to 2, and carrying out mixing reaction for 0.1-60 min at the temperature of 40-100 ℃ to ensure that the reaction is complete and obtain the ternary precursor nano-powder with a proper particle size. Preferably, in order to ensure that the reaction system has proper solubility and reaction conditions, the mixing reaction temperature is 60-80 ℃.
Furthermore, in order to prevent the supersaturated crystallization of soluble components such as sodium salt after the solution is mixed, the temperature needs to be kept constant during the mixing process, and if necessary, a proper amount of water with the same temperature can be supplemented to keep the temperature constant during the mixing reaction process. Preferably, the alkaline solution and the precursor metal salt solution are mixed at the same temperature.
S4, precipitation, filter pressing, washing and drying
And S3, discharging the obtained product into a filter pressing container through a container discharge port after the reaction is finished, and carrying out primary filter pressing, wherein in order to ensure the purity of the obtained precursor, the obtained solid matter is washed at least once after the primary filter pressing, and the washing mode is as follows: and adding water into the filter cake after the primary filter pressing for re-pulping, standing and carrying out filter pressing again, and repeating the actions after multiple times of washing until the acid radical content in the filtrate meets the standard (less than or equal to 2000 ppm).
And drying the washed filter cake in a vacuum environment at the temperature of 80-180 ℃ until the water content is less than or equal to 1wt%, so as to obtain nanoscale ternary precursor powder, wherein the particle size of the nanoscale ternary precursor powder is 20-200 nm under an electron microscope.
S4, spheroidizing
And mixing lithium hydroxide particles and ternary precursor nano powder according to the Li/Me of 1-1.06 for spheroidization, and loading the ternary precursor nano powder on the lithium hydroxide particles to obtain a primary particle material. Li/Me indicates the ratio of the lithium element to the sum of the other metal elements.
Preferably, the spheronization process is performed in mechanical fusion. The mechanical fusion combines the balling and the high mixing into one process, and simplifies the preparation process of the ternary cathode material. Preferably, the mechanical fusion is performed on a fusion machine, and the process parameters of the fusion machine during fusion are set as follows: the fusion parameters are set as: the rotating speed is 700-900 rpm/min, and the fusion time is 10-50 min; the rotating speed is 900-1100 rpm/min, and the fusion time is 2-4 min. Further comprises the following steps: feeding at 40-60 rpm/min; mixing materials at 300-400 rpm/min for 4-6 min; fusing at 700-900 rpm/min for 15-25 min; performing intensive fusion at 900-1100 rpm/min for 2-4 min; discharging at 40-60 rpm/min.
The general settings are as follows: adding materials at 50 rpm/min; mixing at 350 rpm/min for 5 min; fusing at 800 rpm/min for 20 min; performing intensive fusion at 1000 rpm/min for 3 min; discharging at 50 rpm/min.
S5, pre-sintering and high-temperature sintering
The high-temperature sintering of the sphericized mixture can be directly carried out according to the conventional process of the ternary cathode material, or the formal high-temperature sintering can be carried out after low-temperature presintering, and thus, the description is omitted.
The ternary cathode material provided by the embodiment of the application is prepared by the preparation method provided by the embodiment of the application.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
And (2) rapidly mixing 20mol/L sodium hydroxide solution with the same volume with 2.5mol/L nickel-cobalt-manganese sulfate mixed solution (the molar ratio of Ni/Co/Mn = 5/2/3) at 60 ℃, carrying out mixed reaction for 30s, and carrying out pressure filtration, washing and vacuum drying after the reaction is finished, wherein the drying temperature is 120 ℃ to obtain the ternary precursor nano powder.
Mixing lithium hydroxide particles with the diameter of D50=500 μm with the ternary precursor nano powder prepared in the above step according to the Li/Me of 1, and placing the mixture in a fusion machine, wherein the technological parameters of the fusion machine during fusion are as follows: adding materials at 50 rpm/min; mixing materials at 350 rpm/min for 5 min; fusing at 800 rpm/min for 20 min; performing intensive fusion at 1000 rpm/min for 3 min; discharging at 50rpm/min to obtain the ternary cathode material.
Example 2
And (2) rapidly mixing 4mol/L sodium carbonate solution and 2.5mol/L nickel-manganese sulfate mixed solution (the molar ratio of Ni/Mn = 1/3) with the same volume at 60 ℃, carrying out mixing reaction for 5min, and carrying out pressure filtration, washing and vacuum drying after the reaction is finished, wherein the drying temperature is 150 ℃ to obtain the ternary precursor nano powder.
Mixing lithium hydroxide particles with the diameter of D50=500 μm with the ternary precursor nano powder prepared in the above step according to the Li/Me of 1, and placing the mixture in a fusion machine, wherein the technological parameters of the fusion machine during fusion are as follows: adding materials at 50 rpm/min; mixing materials at 350 rpm/min for 5 min; fusing at 800 rpm/min for 20 min; performing intensive fusion at 1000 rpm/min for 3 min; the material was discharged at 50 rpm/min. Obtaining the ternary cathode material.
Example 3
And (2) rapidly mixing 20mol/L sodium hydroxide solution with the same volume with 2.5mol/L cobalt manganese sulfate mixed solution (the molar ratio Co/Mn = 2/3) at 60 ℃, carrying out mixing reaction for 60min, and carrying out pressure filtration, washing and vacuum drying after the reaction is finished, wherein the drying temperature is 180 ℃ to obtain the ternary precursor nano powder.
Mixing lithium hydroxide particles with D50=500 μm with the ternary precursor nano powder prepared in the previous step according to the Li/Me of 1.06, and placing the mixture in a fusion machine, wherein the process parameters of the fusion machine during fusion are set as follows: adding materials at 50 rpm/min; mixing materials at 350 rpm/min for 5 min; fusing at 800 rpm/min for 20 min; performing intensive fusion at 1000 rpm/min for 3 min; discharging at 50 rpm/min. Obtaining the ternary cathode material.
Examples 4 and 5
Examples 4, 5 are essentially the same as example 3, except that:
example 4: the technological parameters of the fusion machine during fusion are set as follows: adding materials at 50 rpm/min; mixing materials at 350 rpm/min for 5 min; fusing at 900rpm/min for 10 min; strengthening fusion at 1100 rpm/min for 2 min; discharging at 50 rpm/min.
Example 5: the technological parameters of the fusion machine during fusion are set as follows: adding materials at 50 rpm/min; mixing materials at 350 rpm/min for 5 min; fusing at 700 rpm/min for 50 min; performing intensive fusion at 900rpm/min for 4 min; discharging at 50 rpm/min.
Example 6
This example is substantially the same as example 1 except that the concentration of the alkaline solution was 30mol/L, the concentration of the nickel cobalt manganese sulfate mixed solution was 3mol/L, the mixing reaction temperature was 90 ℃ and the mixing reaction time was 10 seconds.
Example 7
The present example is substantially the same as example 1 except that the concentration of the alkaline solution is 25mol/L, the concentration of the nickel cobalt manganese sulfate mixed solution is 3mol/L, the mixing reaction temperature is 80 ℃ and the mixing reaction time is 2 min.
Comparative example 1
This comparative example is essentially the same as example 1 except that the mixing reaction time was 2 hours.
Comparative example 2
This comparative example is substantially the same as example 1 except that the concentration of the sodium hydroxide solution was 5mol/L and the concentration of the nickel cobalt manganese sulfate mixed solution was 2 mol/L.
Comparative example 3
The comparative example has the same chemical composition as the target ternary cathode material to be prepared in example 1, and is different only in that a ternary precursor is prepared according to a conventional process, and then is mixed with lithium salt and then is sintered at a high temperature.
Experimental example 1
The particle size of the ternary precursor powder obtained in the preparation processes of examples 1 to 7 and comparative examples 1 and 2 was measured and recorded in the following table.
Figure P_220614095155948_948962001
As can be seen from the above table, the ternary precursor powder obtained in the process of preparing the ternary cathode material in the embodiment of the present application is nano-scale and has a smaller particle size, while the mixing reaction time in comparative example 1 is longer, the obtained ternary precursor powder has a significantly larger particle size and does not belong to the nano-scale, and the ternary precursor powder prepared by the comparative example 2 with a lower concentration of the sodium hydroxide solution has a significantly larger particle size and does not belong to the nano-scale.
Experimental example 2
The ternary precursor powder obtained in the preparation processes of the example 1 and the comparative examples 1 and 2 is placed under a scanning electron microscope to shoot a microstructure diagram, wherein SEM images are shown in figures 1-4, and figures 1 and 2 are respectively 10 ten thousand times SEM image and 20 ten thousand times SEM image of the ternary precursor powder prepared in the example 1; fig. 3 and 4 are SEM images of the ternary precursor powders prepared in comparative examples 1 and 2, respectively, magnified by 1 ten thousand times. The microstructure of the ternary cathode material prepared in example 1 was photographed under a scanning electron microscope, and is shown in fig. 5.
It can be seen from fig. 1 and 2 that the precursor size in example 1 is significantly nanoscale with smooth edges. The precursor powder prepared by the comparative examples 1 and 2 has a significantly larger particle size and does not reach the nanometer level.
As can be seen from fig. 5, the ternary cathode material prepared by the method provided in example 1 has uniform particle size distribution and smaller size.
Experimental example 3
The ternary cathode material 523 prepared in examples 1 to 7 and comparative example 3 was assembled into a CR2032 coin cell and tested for specific discharge capacity. The results are recorded in table 2.
Figure P_220614095156027_027626001
As can be seen from the above table, the performance of the ternary cathode material prepared in example 1 of the present application is not inferior to that of the ternary cathode material prepared by the existing preparation method, and the nickel-cobalt-manganese ternary cathode materials prepared in examples 1, 2, 6, and 7 have higher specific volumes; examples 3 to 5 have low specific volumes because they produced ternary cobalt-manganese positive electrode materials, which did not contain nickel.
In summary, according to the preparation method of the ternary cathode material provided by the application, the nanoscale ternary precursor powder can be obtained by reasonably designing the concentration of the reaction raw materials and the reaction time, the nanoscale ternary precursor powder is compounded with the lithium source, the ternary precursor powder is loaded on the lithium source in the spheroidization process to obtain the primary particle material, and finally sintering is performed to realize the preparation of the ternary cathode material. The whole process is simple and quick; the particle size of the lithium hydroxide is not strictly required, the refined lithium hydroxide powder is not needed, and the problem of precursor crushing is not needed to be worried about; the nano-scale precursor has high reaction activity, and the lithium source and the precursor have good automatic dispersion effect.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a ternary cathode material is characterized by comprising the following steps:
mixing an alkaline solution with the concentration of 20-30 mol/L hydroxyl and a precursor metal salt solution with the concentration of 2.5-3 mol/L according to the molar ratio of the hydroxyl in the alkaline solution to the metal ions in the precursor metal salt solution being not less than 2, carrying out mixing reaction for 0.1-60 min, removing water from the obtained precipitate after the reaction is finished to obtain ternary precursor nano powder, wherein the chemical formula of the obtained ternary precursor nano powder is NixCoyMn(1-x-y)(OH)2Wherein 0 is less than or equal to x<1，0≤y<1, and 0<x+y<1；
Mixing lithium hydroxide and the ternary precursor nano powder for spheroidization, loading the ternary precursor nano powder on lithium hydroxide particles to obtain a primary particle material, and mixing the lithium hydroxide particles and the ternary precursor nano powder according to the Li/Me of 1-1.06, wherein the Li/Me is the molar ratio of the lithium element to the sum of other metal elements;
the spheroidization is carried out on a fusion machine, and fusion parameters are set as follows: feeding at 40-60 rpm/min; mixing materials at 300-400 rpm/min for 4-6 min; fusing at 700-900 rpm/min for 15-25 min; performing intensive fusion at 900-1100 rpm/min for 2-4 min; discharging at 40-60 rpm/min;
sintering the primary particulate material.
2. The method for preparing a ternary cathode material according to claim 1, wherein a mixing reaction process is kept at a constant temperature; the mixing reaction temperature is 40-100 ℃.
3. The method for preparing a ternary cathode material according to claim 1 or 2, wherein the mixing reaction of the alkaline solution and the precursor metal salt solution is performed under a protective atmosphere, and the protective atmosphere is nitrogen or an inert gas.
4. The preparation method of the ternary cathode material according to claim 1 or 2, wherein the ternary precursor nano-powder is obtained by washing the obtained precipitate at least once after the reaction of the alkaline solution and the precursor metal salt solution is finished and removing water.
5. The method for preparing a ternary cathode material according to claim 1 or 2, wherein the precursor metal salt solution is a sulfate solution, a nitrate solution, an acetate solution, or a hydrochloride solution;
the alkaline solution is a solution with solute of at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
6. A ternary positive electrode material, characterized by being produced by the production method according to any one of claims 1 to 5.
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