CN112357975A - Preparation method of hollow ternary cathode material precursor and prepared ternary cathode material precursor - Google Patents
Preparation method of hollow ternary cathode material precursor and prepared ternary cathode material precursor Download PDFInfo
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Abstract
The invention discloses a preparation method of a hollow ternary anode material precursor, which comprises the steps of preparing a raw material metal salt solution, an alkali liquor, a complexing agent solution and hydrogen peroxide, adding the raw material metal salt solution, the alkali liquor, ammonia water and the hydrogen peroxide into a reaction kettle for coprecipitation reaction, and continuously introducing inert protective gas into the reaction kettle in the reaction process; after reacting for 1-5h, stopping the continuous reaction of hydrogen oxide, and stopping feeding when the particle size grows to the target particle size to obtain the hollow ternary cathode material precursor. The method comprises the steps of introducing hydrogen peroxide in the reaction process, wherein the hydrogen peroxide is uniformly distributed in the reaction material, heating the reaction material in a reaction kettle to generate a large amount of oxygen bubbles, so that the precipitation reaction of a precursor is generated at a gas-liquid phase interface, the bubbles are separated from the system along with the stirring along with the generation of the reaction, a hollow structure is formed in a precipitate, and the hydrogen peroxide is uniformly distributed in the reaction material, so that the prepared precursor has uniform hollow particle size and high tap density.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a preparation method of a hollow ternary cathode material precursor.
Background
At present, the lithium ion battery occupies a larger market share in the field of wide portable electronic equipment by virtue of the advantages of high specific capacity, long cycle life, low self-discharge rate, no memory effect, environmental friendliness and the like, and is generally recognized as the most development potential power battery for the electric vehicle. The ternary nickel-cobalt-manganese/aluminum cathode material is an important lithium ion battery cathode material, has the important advantages of better performance than lithium cobaltate, lower cost than lithium cobaltate, higher energy density than lithium iron phosphate and the like, and gradually becomes a mainstream cathode material of an automobile power battery. In order to better exert the excellent performance of the ternary cathode material, the preparation of the precursor is crucial to the production of the ternary cathode material, and the physical and chemical indexes of the final sintered product are directly determined by the quality (morphology, particle size distribution, specific surface area, impurity content, tap density and the like) of the precursor. The preparation method of the ternary anode material precursor mainly adopts a hydroxide coprecipitation process, and comprises the steps of dissolving raw materials in deionized water, mixing according to a certain molar ratio, and then using NaOH as a precipitator and ammonia water as a complexing agent to prepare the high-density spherical hydroxide precursor. For example, a salt solution prepared by nickel sulfate, cobalt sulfate, manganese sulfate/aluminum sulfate according to a certain proportion, alkali liquor and a complexing agent are added into a reaction kettle at the same time, coprecipitation is carried out under a proper reaction condition, and then a required product is obtained after washing, drying and screening, wherein the coprecipitation is a key stage for controlling the shape and structure of a precursor. For the ternary cathode material, the hollow ternary cathode material can increase the contact area between the material and the electrolyte, thereby improving the output performance of the battery and improving the rate capability of the lithium ion battery.
Preparing a hollow ternary cathode material firstlyA hollow ternary cathode material precursor is prepared. At present, the preparation of the hollow ternary cathode material precursor mainly adopts a template method and a kernel oxidation method, wherein the template method has high production cost and is not beneficial to mass production. The nuclear oxidation method is only suitable for NCM products, but not for NCA products, and the method needs to adopt an oxidizing atmosphere at the early stage of precursor preparation to ensure that Mn is added2+Is oxidized to Mn3+The crystallinity of coprecipitation is reduced, so that a loose hollow-like structure is formed in the precursor, but reaction conditions such as oxidation degree and the like are extremely difficult to control in specific production, and the tap density of the obtained product is low.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a precursor of a hollow ternary cathode material, wherein the precursor obtained by the method has controllable hollow particle size and high tap density.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a hollow ternary cathode material precursor comprises the following steps:
s1: preparing raw material metal salt solution, alkali liquor, complexing agent solution and hydrogen peroxide, adding the raw material metal salt solution, the alkali liquor, ammonia water and the hydrogen peroxide into a reaction kettle for coprecipitation reaction, controlling the oxygen content in the reaction kettle to be 1000-30000 ppm, and continuously introducing inert protective gas into the reaction kettle in the reaction process;
s2: after reacting for 1-5h, stopping continuously reacting by hydrogen oxide, stopping feeding when the particle size grows to the target particle size to obtain a solution containing a precursor material, and then aging, washing, drying, screening and deironing to obtain a hollow ternary cathode material precursor;
controlling the pH value of the reaction system to be 10.0-12.0, the ammonia value to be 3-15 g/L and the temperature to be 40-80 ℃.
The introduction of hydrogen peroxide is suspended when the hollow particles grow to the desired size.
Further, the feeding flow rate of the metal salt solution in the step S1 is 0-30 mL/min, and the feeding flow rate of the metal salt solution in the step S2 is 1.5-2 times of the feeding flow rate of the metal salt solution in the step S1.
Further, the stirring speed in the step S1 is 100-900rpm, and the stirring speed in the step S2 is 100rpm higher than that in the step S1.
Further, in the step S2, when the precursor product grows to the target hollow particle size, the hydrogen peroxide is stopped.
Further, the total concentration of metal ions in the metal salt solution is 1-2.5 mol/L, and the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt.
Further, the metal salt solution comprises a nickel-cobalt salt solution and an aluminum salt solution, the total concentration of metal ions in the nickel-cobalt salt solution is 1-2.5 mol/L, and the concentration of aluminum in the aluminum salt solution is 0.05-0.3 mol/L.
Further, the inert protective gas is nitrogen.
The precursor of the ternary cathode material is prepared by the preparation method of the precursor of the hollow ternary cathode material.
The invention has the beneficial effects that: the method comprises the steps of introducing hydrogen peroxide in the reaction process, wherein the hydrogen peroxide is uniformly distributed in the reaction material, heating the reaction material in a reaction kettle to generate a large amount of oxygen bubbles, so that the precipitation reaction of a precursor is generated at a gas-liquid phase interface, the bubbles are separated from the system along with the stirring along with the generation of the reaction, a hollow structure is formed in a precipitate, and the hydrogen peroxide is uniformly distributed in the reaction material, so that the prepared precursor has uniform hollow particle size and high tap density.
Drawings
FIG. 1 is a sectional electron micrograph of a ternary precursor particle prepared in example 1;
FIG. 2 is a sectional electron micrograph of a ternary precursor particle prepared in example 2;
FIG. 3 is a sectional electron micrograph of a ternary precursor particle prepared in example 3;
FIG. 4 is a sectional electron micrograph of the ternary precursor particles prepared in comparative example 1;
FIG. 5 is a sectional electron micrograph of the ternary precursor particles prepared in comparative example 2;
FIG. 6 is a sectional electron micrograph of a ternary precursor particle prepared in comparative example 3;
fig. 7 is a sectional electron microscope image of the ternary precursor particles prepared in comparative example 4.
Detailed Description
The invention is further explained below with reference to the drawings and the embodiments.
Example 1:
simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water, sodium hydroxide and hydrogen peroxide into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min;
the hollow diameter required by product design is 2 μm, hydrogen peroxide is continuously introduced for 1 hour when the reaction starts, the oxygen content in the reaction kettle is kept at 20000ppm, the introduction of the hydrogen peroxide is stopped after 1 hour, the rotating speed is increased to 900rpm, the flow is increased to 1.5 times of the original flow, the temperature is kept at 50 +/-0.5 ℃, the ammonia value is 8 +/-0.5 g/L, and the pH value is 11.8 +/-0.1 in the process;
after the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, then enabling the pH value of the filtrate to be less than 9, drying the filter cake for 24 hours, screening and demagnetizing the filtrate to obtain a hollow ternary precursor material, wherein the cross section of the ternary precursor is shown in figure 1, and the specific surface area of the hollow ternary precursor is detected to be 15.89m2(g) tap density of 1.57g/cm3。
Example 2:
simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water, sodium hydroxide and hydrogen peroxide into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min;
the hollow diameter required by product design is 2 μm, hydrogen peroxide is continuously introduced for 1 hour when the reaction starts, the oxygen content in the reaction kettle is kept at 10000ppm, the introduction of hydrogen peroxide is stopped after 1 hour, the rotating speed is increased to 900rpm, the flow rate is increased to 1.5 times of the original flow rate, and the temperature is kept at 50 +/-0.5 ℃, the ammonia value is 8 +/-0.5 g/L, and the pH value is 11.8 +/-0.1 in the process.
After the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, then enabling the pH value of the filtrate to be less than 9, drying the filter cake for 24 hours, screening and demagnetizing the filtrate to obtain a hollow ternary precursor material, wherein the cross section of the ternary precursor is shown in figure 2, and the specific surface area of the hollow ternary precursor is 14.81m2(g) tap density of 1.64g/cm3。
Example 3:
simultaneously flowing nickel cobalt sulfate solution, sodium metaaluminate solution, ammonia water, sodium hydroxide and hydrogen peroxide into a reaction kettle, introducing nitrogen for protection, setting stirring at 800rpm, setting the temperature of a reaction system at 50 ℃, setting the ammonia value at 10g/L, setting the pH value at 12.1, setting the total concentration of metal ions in the nickel cobalt sulfate solution at 2mol/L, setting the concentration of the sodium metaaluminate solution at 0.1mol/L, setting the mass percentage concentration of the sodium hydroxide solution at 32%, setting the mass percentage concentration of the ammonia water at 21%, and setting the feeding amount of the nickel cobalt sulfate at 19ml/min, wherein the molar ratio of the feeding of the nickel sulfate, the cobalt sulfate and the sodium metaaluminate is 85:10: 5;
the required hollow diameter of the product is 3 mu m, hydrogen peroxide is continuously introduced for 2 hours when the reaction is started, the oxygen content in the reaction kettle is kept at 25000ppm, the introduction of the hydrogen peroxide is stopped after two hours, the rotating speed is increased to 900rpm, the flow is increased to 1.5 times of the original flow, and the temperature is kept at 50 +/-0.5 ℃, the ammonia value is 10 +/-0.5 g/L, and the pH value is 12.1 +/-0.1 in the process;
after the grain diameter reaches 12 mu m, the kettle material is placed in an aging kettle for aging for 5 hours, the material is pulped by 1mol/L sodium hydroxide solution after being filtered,filtering and washing with 40 deg.C pure water for one time, filtering to obtain filtrate with pH value less than 9, oven drying filter cake for 24h, sieving, and demagnetizing to obtain hollow ternary precursor material with ternary precursor cross section as shown in FIG. 3, and specific surface area of the hollow ternary precursor material detected to be 18.0m2(g) tap density of 1.84g/cm3。
Comparative example 1: (the oxygen content in the reaction vessel was 500ppm, the remainder was the same as in example 1)
Simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water, sodium hydroxide and hydrogen peroxide into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min;
the hollow diameter required by product design is 2 μm, hydrogen peroxide is continuously introduced for 1 hour when the reaction is started, the oxygen content in the reaction kettle is kept at 500ppm, the introduction of the hydrogen peroxide is stopped after 1 hour, the rotating speed is increased to 900rpm, the flow rate is increased to 1.5 times of the original flow rate, and the temperature is kept at 50 +/-0.5 ℃, the ammonia value is 8 +/-0.5 g/L, and the pH value is 11.8 +/-0.1 in the process.
After the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, drying a filter cake for 24 hours, screening and demagnetizing the filter cake to obtain a ternary precursor material, and detecting that the specific surface area of the ternary precursor is 8.53m2(g) tap density of 1.77g/cm3The specific surface area is only 8.53m due to the small amount of hydrogen peroxide introduced2(ii)/g, as shown in FIG. 4, no hollow structure is formed in the cross-sectional view.
Comparative example 2: (the oxygen content in the reaction vessel was 35000ppm, as in example 1.)
Simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water, sodium hydroxide and hydrogen peroxide into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min;
the hollow diameter required by product design is 2 μm, hydrogen peroxide is continuously introduced for 1 hour when the reaction is started, the oxygen content in the reaction kettle is maintained at 35000ppm, the introduction of hydrogen peroxide is stopped after 1 hour, the rotating speed is increased to 900rpm, the flow rate is increased to 1.5 times of the original flow rate, and the temperature is maintained at 50 +/-0.5 ℃, the ammonia value is 8 +/-0.5 g/L, and the pH value is 11.8 +/-0.1 in the process.
After the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, drying a filter cake for 24 hours, screening and demagnetizing the filter cake to obtain a ternary precursor material, and detecting that the specific surface area of the ternary precursor is 17.2m2(g) tap density of 1.20g/cm3Mn in the slurry due to too high oxygen content2+Oxidation to Mn3+The precursor structure is changed, so that the product particles are loose as a whole, the specific surface area is increased, and the non-hollow structure is observed on the section.
Comparative example 3: introducing an oxidizing gas
Simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water, sodium hydroxide and oxygen into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min;
the hollow diameter required by product design is 2 μm, the reaction starts to continuously introduce the oxygen for 1 hour, the oxygen content in the reaction kettle is kept at 20000ppm, the introduction of the oxygen is stopped after 1 hour, the rotating speed is increased to 900rpm, the flow is increased to 1.5 times of the original flow, the temperature is kept at 50 +/-0.5 ℃, the ammonia value is 8 +/-0.5 g/L, and the pH value is 11.8 +/-0.1 in the process;
after the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, then enabling the pH value of the filtrate to be less than 9, drying the filter cake for 24 hours, screening and demagnetizing the filter cake to obtain a ternary precursor material, wherein as shown in figure 6, no obvious hollow structure is formed in the section observation, and the specific surface area of the ternary precursor is detected to be 10.76m2(g) tap density of 1.53g/cm3。
Comparative example 4: (Hydrogen peroxide)
Simultaneously flowing nickel cobalt manganese sulfate solution, ammonia water and sodium hydroxide into a reaction kettle, introducing nitrogen for protection, setting stirring to be 800rpm, setting the temperature of a reaction system to be 50 ℃, setting the ammonia value to be 8.0g/L and setting the pH value to be 11.8, wherein the molar ratio of nickel, cobalt and manganese in the nickel cobalt manganese sulfate solution is 5:2:3, the concentration of total metal ions in the nickel cobalt manganese sulfate solution is 2mol/L, the mass percentage concentration of the sodium hydroxide solution is 32%, the mass percentage concentration of the ammonia water is 21%, and the feeding amount of the nickel cobalt manganese sulfate solution is 30 ml/min; after the particle size reaches 6 mu m, placing the kettle material in an aging kettle for aging for 5 hours, filtering the material, slurrying the material with 1mol/L sodium hydroxide solution, filtering and washing the material once with pure water at 40 ℃, then, the pH value of the filtrate is less than 9, drying the filter cake for 24 hours, screening and demagnetizing the filter cake to obtain a ternary precursor material, wherein the ternary precursor material has no hollow structure as shown in figure 7, and the specific surface area of the ternary precursor is 8.02m2(g) tap density of 18.13g/cm3。
Claims (8)
1. The preparation method of the precursor of the hollow ternary cathode material is characterized by comprising the following steps of:
s1: preparing raw material metal salt solution, alkali liquor, complexing agent solution and hydrogen peroxide, adding the raw material metal salt solution, the alkali liquor, ammonia water and the hydrogen peroxide into a reaction kettle for coprecipitation reaction, controlling the oxygen content in the reaction kettle to be 1000-30000 ppm, and continuously introducing inert protective gas into the reaction kettle in the reaction process;
s2: after reacting for 1-5h, stopping continuously reacting by hydrogen oxide, stopping feeding when the particle size grows to the target particle size to obtain a solution containing a precursor material, and then aging, washing, drying, screening and deironing to obtain a hollow ternary cathode material precursor;
controlling the pH value of the reaction system to be 10.0-12.0, the ammonia value to be 3-15 g/L and the temperature to be 40-80 ℃.
2. The preparation method of the hollow ternary cathode material precursor according to claim 1, wherein the preparation method comprises the following steps: the feeding flow rate of the metal salt solution in the S1 step is 0-30 mL/min, and the feeding flow rate of the metal salt solution in the S2 step is 1.5-2 times of the feeding flow rate of the metal salt solution in the S1 step.
3. The method for preparing a precursor of a hollow ternary cathode material according to claim 1 or 2, wherein the method comprises the following steps: the stirring speed in the step S1 is 100-900rpm, and the stirring speed in the step S2 is 100rpm higher than that in the step S1.
4. The preparation method of the hollow ternary cathode material precursor according to claim 3, wherein the preparation method comprises the following steps: in the step S2, when the precursor product grows to the target hollow particle size, the hydrogen oxidation is stopped.
5. The method for preparing a precursor of a hollow ternary cathode material according to claim 1 or 2, wherein the method comprises the following steps: the total concentration of metal ions in the metal salt solution is 1-2.5 mol/L, and the metal salt solution is an aqueous solution containing nickel salt, cobalt salt and manganese salt.
6. The method for preparing a precursor of a hollow ternary cathode material according to claim 1 or 2, wherein the method comprises the following steps: the metal salt solution comprises a nickel-cobalt salt solution and an aluminum salt solution, wherein the total concentration of metal ions in the nickel-cobalt salt solution is 1-2.5 mol/L, and the concentration of aluminum in the aluminum salt solution is 0.05-0.3 mol/L.
7. The preparation method of the hollow ternary cathode material precursor according to claim 1, wherein the preparation method comprises the following steps: the inert protective gas is nitrogen.
8. The precursor of the hollow ternary cathode material prepared by the preparation method of the precursor of the hollow ternary cathode material according to claims 1-7.
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| WO2024055514A1 (en) * | 2022-09-13 | 2024-03-21 | 广东邦普循环科技有限公司 | High-nickle ternary precursor, preparation method therefor, and use thereof |
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