CN112357970B - Preparation method of homogeneous phase aluminum-doped small-particle-size cobaltosic oxide - Google Patents
Preparation method of homogeneous phase aluminum-doped small-particle-size cobaltosic oxide Download PDFInfo
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Abstract
The invention relates to the technical field of preparation of lithium ion battery precursor cobaltosic oxide, in particular to a preparation method of homogeneous phase aluminum-doped cobaltosic oxide with small particle size. The method adopts the composite complexing agent to balance Co 2+ And Al 3+ Reaction Rate in the System, co 2+ And Al 3+ Homogeneous coprecipitation can be achieved, and the purpose of uniform aluminum doping is achieved; the combination degree of the complexing agent and the metal ions can be effectively controlled by adopting the composite complexing agent, so that the concentration of the metal ions in the tail liquid is reduced. The granularity of the aluminum-doped cobaltosic oxide prepared by the method is 2.0-6.0 mu m, the morphology is similar to a sphere, and the tap density is 2.6-3.0 g/cm 3 The mass percentage of Al is 0.1-1.2%.
Description
Technical Field
The invention relates to a preparation method of a precursor cobaltosic oxide of a lithium ion battery for high voltage, in particular to a preparation method of homogeneous phase aluminum-doped cobaltosic oxide with small particle size.
Background
The cobaltosic oxide is used for preparing a lithium cobaltate anode material, and the terminal of the cobaltate anode material is applied to batteries of 3C electronic products such as high-capacity mobile phones, notebook computers, digital cameras and the like. Along with the continuous progress of technology, the consumption level of people is continuously improved, the requirements on the performance such as the endurance capacity, the charging rate and the like of electronic products are also higher and higher, the large capacity, the high multiplying power and the like of a lithium ion battery mainly depend on the performance of a positive electrode material lithium cobaltate, and the energy density of the lithium cobaltate is required to be improved in two ways: first doping with other elements such as: mg, al, zr, ti, ni, mn and the like to improve the energy density of the lithium ion battery by improving the charging cut-off voltage, and to improve the compaction density by improving the mixing density of the cobaltosic oxide with the second size, wherein the main flow grain size of the cobaltosic oxide with the small grain size is 3-6 mu m at present, and the requirements of the market on the grain size of the small grains are smaller and smaller in the future.
The 4.45V high-voltage lithium cobaltate precursor is aluminum-doped cobaltate, the charging cut-off voltage is improved by an aluminum doping mode, and the energy density is improved by doping cobaltate with different particle sizes. At present, aluminum-doped cobaltosic oxide with large and small particle sizes is prepared by adopting a wet method carbonate synthesis technical route and calcining at high temperature.
The carbonate technical route has the following defects: 1. ammonium bicarbonate is adopted as a precipitator, is unstable and is easy to decompose to generate ammonia gas, and the environment is affected; 2. the pH value of the ammonium bicarbonate precipitated cobalt is low, and the decomposed ammonia can complex Co to a certain extent 2+ Incomplete Co metal ion precipitation is caused, the concentration of metal ions in wastewater is increased, the wastewater treatment cost is increased, and a certain pressure is applied to the environment; 3. carbonate systems generally have poor uniformity of aluminum incorporation, especially at high levels of aluminum incorporation.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of homogeneous aluminum-doped cobaltosic oxide with small particle size, which has the advantages of uniform aluminum doping, complete metal ion precipitation, low wastewater treatment cost and low environmental pressure.
In order to achieve the above purpose, the preparation method of the homogeneous phase aluminum-doped cobaltosic oxide with small particle size comprises the following steps:
1. adding aluminum sulfate octadecatriend a composite complexing agent into a cobalt sulfate solution together, and uniformly stirring to prepare cobalt-aluminum mixed solution; the molar mass ratio of the aluminum ions to the composite complexing agent to the cobalt ions in the cobalt-aluminum mixed solution is as follows: (0.002-0.017): (0.001-0.01): 1, the cobalt ion concentration is 110-150 g/L;
2. adding base liquid into the reaction vessel, immersing stirring blade in the base liquid, and introducing compressed air with air flow of 0.7-2.1 m 3 And/h, wherein the temperature is 68-75 ℃; adding the cobalt-aluminum mixed solution and the alkali liquor prepared in the step 1 at the same time under the stirring rotation speed of 400-450 rpmThe mixture is put into a reaction vessel, the pH of the reaction and the granularity of the slurry are monitored, wherein the pH is controlled to be 10.6-11.5;
3. stopping adding the cobalt-aluminum mixed solution when the granularity of the slurry reaches the target granularity of 2-6 mu m, and continuously and independently adding the alkali solution until the pH value of the slurry is 11.8-12.0;
4. cooling the slurry to 30-40 ℃ by adopting circulating cooling water, stirring for 30min, and filtering and washing the slurry;
5. and (3) placing the washed material into a rotary kiln, and calcining at a high temperature of 700-820 ℃, removing iron and sieving through vibration to finally obtain the small-particle-size cobaltosic oxide with compact particles, good dispersibility and uniform aluminum distribution.
Preferably, the complex complexing agent is two or more of isopropanol, glycine, glutamic acid, sodium sulfonate, malic acid and ethanolamine;
preferably, the compound complexing agent is formed by compounding isopropanol and glycine;
preferably, the compound complexing agent is compounded by glutamic acid and sodium sulfonate;
as a further preferable mode, the compound complexing agent is formed by compounding malic acid and ethanolamine;
preferably, in the step 2, a sodium hydroxide solution with the concentration of 0.5M is used as a base solution;
preferably, deionized water is added as base solution in the step 2, and sodium hydroxide is used for adjusting the pH value of the base solution to 11.0-12.0;
preferably, the alkali liquor adopts sodium hydroxide solution with the concentration of 80-120 g/L;
preferably, the slurry particle size is measured every 2 hours and the pH is measured every hour during the reaction in the step 2;
the granularity of the aluminum-doped cobaltosic oxide prepared by the method is 2.0-6.0 mu m, the morphology is similar to a sphere, and the tap density is 2.6-3.0 g/cm 3 The mass percentage of Al is 0.1-1.2%.
The tail liquid filtered by the slurry synthesized by the method mainly contains Co 2+ 、Al 3+ 、Na + Etc. 3 kinds of metal ions and SO 4 2- Anions, wherein the content of Co ions is less than 0.001g/L, the content of Al ions is less than 0.001g/L, the content of COD is less than 0.2g/L and the content of NH3-N is less than 0.015g/L.
The key points of the invention are as follows: first, co can be effectively balanced by adopting a composite complexing agent 2+ And Al 3+ Reaction Rate in the System, co 2+ And Al 3+ Can perform homogeneous coprecipitation, and achieve the purpose of uniform aluminum doping. Secondly, the combination degree of the complexing agent and the metal ions can be effectively controlled by adopting the composite complexing agent, so that the concentration of the metal ions in the tail liquid is reduced. Thirdly, the temperature of the slurry is reduced to 30-40 ℃ before filtration, so that the supersaturation degree of metal ions in the solution can be effectively reduced, and the concentration of the metal ions in the tail liquid is reduced; in addition, the temperature is reduced, the activity of the complexing agent is reduced, the complexing ability of the complexing agent and metal ions is weakened, and more free metal ions are combined with hydroxyl to precipitate. Fourth, when the slurry granularity reaches the target value, the pH is increased, and further precipitation of metal ions can be promoted to be complete. And fifthly, the main component in the tail liquid is sodium sulfate, and sodium sulfate serving as a byproduct can be prepared by an evaporation crystallization technology, so that the wastewater index after sodium sulfate removal meets the emission standard of industrial pollutants of GB25467-2010 copper, cobalt and nickel, and the method belongs to the environment-friendly type.
Drawings
FIG. 1 is a scanning electron microscope image of the cobaltosic oxide obtained in example 1 of the present invention at a magnification of 1000 times;
FIG. 2 is a scanning electron microscope image of the cobaltosic oxide obtained in example 1 of the present invention at a magnification of 3000 times;
FIG. 3 is a scanning electron microscope image of the cobaltosic oxide obtained in example 2 of the present invention at 500 Xmagnification;
FIG. 4 is a scanning electron microscope image of the cobaltosic oxide obtained in example 2 of the present invention at a magnification of 3000 times;
FIG. 5 is a scanning electron microscope image of the cobaltosic oxide obtained in example 3 of the present invention at a magnification of 1000 times;
FIG. 6 is a scanning electron microscope image of the cobaltosic oxide obtained in example 3 of the present invention at a magnification of 3000 times;
Detailed Description
Example 1
(1) Preparing a cobalt sulfate solution of 110g/L, adding 2.713kg of aluminum sulfate octadeca hydrate and 0.11kg of a composite complexing agent mixed by isopropanol and glycine into each cobalt solution, and uniformly stirring;
(2) adding proper deionized water as base solution into a reaction container, regulating pH of the base solution to 11.0 with sodium hydroxide, and introducing compressed air with air flow of 0.7m 3 Adding the prepared cobalt-aluminum mixed solution and 80g/L sodium hydroxide solution into a reaction container at the temperature of 68 ℃ and at the stirring rotation speed of 400rpm, measuring one slurry particle size every 2 hours, measuring pH every hour, and controlling the pH of the process to be 11.5;
(3) stopping adding the cobalt-aluminum mixed solution when the granularity of the slurry reaches the target granularity of 2.0-2.2 mu m, and continuously adding the alkali solution independently until the pH value of the slurry is 11.8-12.0;
(4) after the pH is regulated, cooling the slurry to 30-40 ℃ by adopting circulating cooling water, stirring for 30min, and filtering and washing the slurry;
(5) the materials are washed and then are transferred to a rotary kiln, and are subjected to high-temperature calcination at 740 ℃, iron removal, vibration sieving and packaging;
detection index of cobaltosic oxide: the Co content is 72.75%, the Al content is 0.1128%, and the median diameter D50:2.12 μm, tap density 2.65g/cm 3 The particle size is uniform, and no agglomeration and adhesion are caused.
The content of Co ions in the tail liquid is 0.0006g/L, the content of Al ions is less than 0.0002g/L, the content of COD is 0.1083g/L, and the content of NH3-N is 0.006g/L.
Example 2
(1) Preparing a cobalt sulfate solution with the concentration of 130g/L, adding 15.232kg of aluminum sulfate octadecabydrate and 0.65kg of a compound complexing agent mixed by glutamic acid and sodium sulfonate into each cobalt solution, and uniformly stirring;
(2) adding proper deionized water as base solution into a reaction container, regulating pH of the base solution to 11.5 with sodium hydroxide, and introducing compressed air with air flow of 1.4m 3 Adding the prepared cobalt-aluminum mixture and 100g/L sodium hydroxide solution into a reaction vessel at the temperature of 72 ℃ at the stirring speed of 420rpm, and measuring one slurry every 2 hoursParticle size, once per hour pH, process pH was controlled at 11.0;
(3) stopping adding the cobalt-aluminum mixed solution when the granularity of the slurry reaches the target granularity of 3.9-4.1 mu m, and continuously adding the alkali liquor independently until the pH value of the slurry is 11.8-12.0;
(4) after the pH is regulated, cooling the slurry to 30-40 ℃ by adopting circulating cooling water, stirring for 30min, and filtering and washing the slurry;
(5) the materials are washed and then are transferred to a rotary kiln, and are subjected to high-temperature calcination at 780 ℃, iron removal, vibration sieving and packaging.
Detection index of cobaltosic oxide: co content 72.21%, al content 0.6155%, median particle diameter D50:4.08 μm, tap density 2.84g/cm 3 The particle size is uniform, and no agglomeration and adhesion are caused.
The content of Co ions in the tail liquid is 0.0003g/L, the content of Al ions is less than 0.0001g/L, the content of COD is 0.1252g/L, and the content of NH3-N is 0.009g/L.
Example 3
(1) Preparing 150g/L cobalt sulfate solution, adding 31.450kg of aluminum sulfate octadeca hydrate and 1.5kg of a composite complexing agent mixed by malic acid and ethanolamine into each cobalt solution, and uniformly stirring;
(2) adding proper deionized water as base solution into a reaction container, regulating pH of the base solution to 12.0 with sodium hydroxide, and introducing compressed air with air flow of 2.1m 3 Adding the prepared cobalt-aluminum mixed solution and 120g/L sodium hydroxide solution into a reaction container at the temperature of 75 ℃ and at the stirring rotation speed of 450rpm, measuring one slurry particle size every 2 hours, measuring pH every hour, and controlling the pH of the process to be 10.6;
(3) stopping adding the cobalt-aluminum mixed solution when the granularity of the slurry reaches the target granularity of 5.8-6.0 mu m, and continuously adding the alkali solution independently until the pH value of the slurry is 11.8-12.0;
(4) after the pH is regulated, cooling the slurry to 30-40 ℃ by adopting circulating cooling water, stirring for 30min, and filtering and washing the slurry;
(5) the materials are washed and then are transferred to a rotary kiln, and are subjected to high-temperature calcination at 820 ℃, iron removal, vibration sieving and packaging.
Tetraoxy (IV)And (3) detecting the cobalt oxide: co content 71.58%, al content 1.1980%, median particle size D50:5.81 μm, tap density 2.92g/cm 3 The particle size is uniform, and no agglomeration and adhesion are caused.
The content of Co ions in the tail liquid is 0.0001g/L, the content of Al ions is less than 0.0003g/L, the content of COD is 0.1684g/L, and the content of NH3-N is 0.013g/L.
Claims (4)
1. A preparation method of homogeneous phase aluminum-doped small-particle-size cobaltosic oxide is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding aluminum sulfate octadecatriend a composite complexing agent into a cobalt sulfate solution together, and uniformly stirring to prepare cobalt-aluminum mixed solution; the molar mass ratio of the aluminum ions to the composite complexing agent to the cobalt ions in the cobalt-aluminum mixed solution is as follows: (0.002-0.017): (0.001-0.01): 1, the cobalt ion concentration is 110-150 g/L; the compound complexing agent is formed by compounding isopropanol and glycine or by compounding malic acid and ethanolamine;
(2) Adding deionized water into a reaction container as base solution, regulating the pH of the base solution to 11.0-12.0 by sodium hydroxide, submerging stirring blades by the base solution, and introducing compressed air with the air flow of 0.7-2.1 m 3 And/h, wherein the temperature is 68-75 ℃; simultaneously adding the cobalt-aluminum mixed solution and the alkali liquor prepared in the step 1 into a reaction container at a stirring rotation speed of 400-450 rpm, and monitoring the reaction pH and the slurry granularity in the process, wherein the pH is controlled to be 10.6-11.5;
(3) Stopping adding the cobalt-aluminum mixed solution when the granularity of the slurry reaches the target granularity of 2-6 mu m, and continuously and independently adding the alkali solution until the pH value of the slurry is 11.8-12.0;
(4) Cooling the slurry to 30-40 ℃ by adopting circulating cooling water, stirring for 30min, and filtering and washing the slurry;
(5) And (3) placing the washed material into a rotary kiln, and calcining at a high temperature of 700-820 ℃, removing iron, and sieving through vibration to finally obtain the small-particle-size cobaltosic oxide with compact particles, good dispersibility and uniform aluminum distribution.
2. The method for preparing the homogeneous aluminum-doped small-particle-size cobaltosic oxide according to claim 1, which is characterized by comprising the following steps: in the step (2), a sodium hydroxide solution with the concentration of 0.5M is adopted as a base solution.
3. The method for preparing the homogeneous aluminum-doped small-particle-size cobaltosic oxide according to claim 1, which is characterized by comprising the following steps: the alkali liquor adopts sodium hydroxide solution with the concentration of 80-120 g/L.
4. The method for preparing the homogeneous aluminum-doped small-particle-size cobaltosic oxide according to claim 1, which is characterized by comprising the following steps: the slurry particle size was measured every 2 hours and the pH was measured every hour during the reaction of step (2).
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