CN108298596B - Preparation method of large-particle-size doped cobaltosic oxide - Google Patents
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Abstract
The invention provides a preparation method of large-particle-size doped cobaltosic oxide, which comprises the steps of taking a cobalt solution with a certain concentration as a cobalt source, taking a sodium carbonate solution as a precipitator, taking an ammonia water solution as a complexing agent, taking a hydrazine hydrate solution as a reducing agent, taking a mixed solution of a doping element solution and the complexing agent as a doping agent, synthesizing cobalt carbonate with the particle size of 20-30 mu m in a wet method in the shortest time by reducing the generation quantity of crystal nuclei at the initial synthesis stage and the like, and adding the doping solution into a reaction kettle for participating in a reaction at a proper time in the reaction process; after the synthesis is finished, under the condition of a certain pH value, oxidizing the synthesized product into cobalt oxyhydroxide by using a hydrogen peroxide solution with a certain solubility, and then washing, drying and calcining the mixture to obtain a large-particle-size doped cobaltosic oxide product. The process has the advantages that the synthesis time is short and only needs 10-15 hours, the physical and chemical indexes of the product are good, the laser particle size is 15-25 mu m, and the tap density is more than 2.0g/cm3The specific surface area is 1.0-3.0 m2The dopable elements include Ni, Mn, Al, Cu, Ce, Y, Nb and Mg.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of large-particle-size doped cobaltosic oxide for preparing lithium cobaltate serving as a positive electrode material of a lithium ion battery.
Background
The lithium ion battery prepared by taking lithium cobaltate as the anode material has the characteristics of light weight, large capacity, high specific energy, high working voltage, stable discharge, suitability for large-current discharge, good cycle performance, long service life and the like, and is mainly applied to the field of 3C digital codes.
Lithium cobaltate is positively cycled towards high voltage, high compaction and high cycleThe performance is developing, and the requirement for the raw material cobaltosic oxide is higher and higher. Co3O4Is a functional material with special structure and performance, and is Co with conventional grain size (5-10 microns)3O4The market has faced the current situation of gradual shrinkage, large particle size doped with Co3O4The market demand is gradually highlighted. It has become a hot point to study how to prepare high-performance large-particle-size doped cobaltosic oxide.
Chinese patent CN201510881580.4 discloses a method for preparing spherical cobaltosic oxide with large particle size and high density, which comprises the steps of preparing cobalt carbonate through multiple circulation crystallization in the cobalt carbonate synthesis stage, locally decomposing the cobalt carbonate in the low-temperature pre-decomposition stage through sectional thermal decomposition to form a micropore channel, and densifying the particle surface in the high-temperature thermal decomposition stage, thereby obtaining the spherical cobaltosic oxide with large particle size and high density. The method needs repeated circulating crystallization in the cobalt carbonate synthesis stage, has a complex process, and is not beneficial to industrial production. Chinese patent CN201210486483.1 discloses a method for preparing doped spherical cobaltosic oxide, which comprises the steps of doping element ions into a cobalt salt solution to prepare a doped mixed solution, introducing the doped mixed solution, a hydroxide solution and air into a reaction device simultaneously, and continuously stirring to react to prepare the doped spherical cobaltosic oxide. Chinese patent CN200810110753.2 discloses a method for preparing doped cobaltosic oxide, which comprises the steps of doping element ions into a cobalt salt solution to prepare a doped mixed solution, introducing the doped mixed solution and a hydroxide solution containing ammonia water into a reaction device to react, and washing, drying and calcining the mixed solution to prepare the doped spherical cobaltosic oxide. The two preparation methods both adopt hydroxide as a precipitator, are different from the precipitator adopted by the application, and are obviously different from the preparation method of the cobaltosic oxide with large granularity prepared by the application.
Disclosure of Invention
The invention aims to overcome the defects of the technology and provide a preparation method of large-particle-size doped cobaltosic oxide, which is simple and easy to control in the production process, for the field.
The technical scheme of the invention is as follows: a preparation method of large-particle-size doped cobaltosic oxide is characterized by comprising the following specific steps:
a. preparing solution A
Preparing a cobalt solution with the cobalt concentration of 1-2 mol/L as an A solution by using cobalt salt as a raw material;
b. preparing solution B
Preparing a sodium carbonate solution with the concentration of 1-2 mol/L as a B solution, wherein the molar concentration of sodium carbonate in the B solution is the same as that of cobalt in the A solution;
c. preparing solution C
Preparing an ammonia water solution with the concentration of 5-10 mol/L, and adding 5-20 ml of hydrazine hydrate solution with the mass content of 30% into each liter of ammonia water solution to obtain a solution C;
d. preparing solution D
Preparing a hydrogen peroxide solution with the concentration of 5-10 mol/L as a solution D;
e. preparation of solution E
Preparing a sodium hydroxide solution with the concentration of 2-6 mol/L as an E solution;
f. preparing solution F
Preparing a doping element soluble salt solution with the concentration of 5-50 g/L to be an F solution;
g. synthesis reaction
When the synthesis reaction starts, the solution A, the solution B and the solution C are added into a reaction kettle in a parallel flow mode, the solution F is added into the reaction kettle in a proper time according to the chemical property of the doped element compound, the cobalt carbonate synthesis reaction is carried out under stirring, and the ammonia concentration, the reaction temperature, the flow rate of the solution A and the solution B, the stirring intensity and the reaction time in the reaction kettle are strictly controlled in the reaction process;
h. oxidation by oxygen
After the synthesis is finished, simultaneously adding D, E solution into a reaction kettle, oxidizing cobalt carbonate precipitate into cobalt oxyhydroxide under stirring, and strictly controlling the pH value, the reaction temperature and the oxidation time in the oxidation process;
i. filtering, washing and drying
After the oxidation process is finished, filtering, slurrying, washing and drying the material to obtain a large-particle-size doped cobaltosic oxide precursor product;
j. calcination of
And (e) calcining the product obtained in the step (i) under the calcining condition to obtain a large-particle-size doped cobaltosic oxide product.
In the step a, the cobalt salt is one or more of cobalt sulfate, cobalt nitrate or cobalt chloride.
In the step f, the doping element soluble salt is one or more chlorides or nitrates of Ni, Mn, Al, Cu, Ce, Y, Nb and Mg.
In the step g, the solution F is added into the reaction kettle at a proper time according to the chemical property of the doped element compound, the ammonia concentration of the solution in the reaction kettle, the reaction temperature, the flow rates of the solutions A and B, the stirring intensity and the ammonia concentration of the solution in the reaction time are strictly controlled to be 5-10 g/L in the reaction process when the reaction starts, in the reaction process or after the reaction finishes according to the chemical property of the doped element compound, the reaction temperature is 60-80 ℃, the flow rate of the solution A is 0-1 h of the flow rate 100L/h in the reaction time period, the flow rate of the solution A is 200L/h in the reaction time period, the flow rate of the solution A is 2-3 h of the reaction time period is 300L/h, the flow rate of the solution A is 400L/h in the reaction time period, the flow rate of the solution B is 1.0-1.1 times of the flow rate of the solution A after the, the stirring intensity is 200-500 r/min, and the reaction time is 10-15 h.
In the oxidation process, the pH value, the reaction temperature and the oxidation time are strictly controlled to be 10-11, the reaction temperature is 60-80 ℃, and the oxidation time is 1-2 hours.
In the step i, deionized water at 80-100 ℃ is adopted for slurrying and washing the materials, and the drying temperature of the materials is 100-400 ℃.
In the step j, the calcining condition is that the calcining temperature is 700-800 ℃ and the calcining time is 2-5 h under the condition of not introducing oxidizing gas.
The large-particle-size doped cobaltosic oxide product obtained in the step j has the physicochemical indexes that: the laser particle size is 15-25 mu m, and the tap density is not less than 2.0g/cm3The specific surface area is 1.0 to 3.0m2/g、The doping elements comprise Ni, Mn, Al, Cu, Ce, Y, Nb and Mg, the doping amount is 0-2%, and the shape is spherical or spheroidal.
The method is characterized in that: taking a cobalt solution with a certain concentration as a cobalt source, a sodium carbonate solution as a precipitator, an ammonia water solution as a complexing agent, a hydrazine hydrate solution as a reducing agent, and a mixed solution of a doping element solution and the complexing agent as a doping agent, synthesizing cobalt carbonate with the particle size of 20-30 mu m in a wet method in the shortest time by reducing the generation amount of crystal nuclei at the initial synthesis stage, and the like, and adding the doping solution into a reaction kettle for participating in a reaction in a proper time in the reaction process; after the synthesis is finished, under the condition of a certain pH value, oxidizing the synthesized product into cobalt oxyhydroxide by using a hydrogen peroxide solution with a certain solubility, and then washing, drying and calcining the mixture to obtain a large-particle-size doped cobaltosic oxide product.
The invention has the beneficial effects that: according to the method, the generation quantity of cobalt carbonate crystal nuclei is reduced by reducing the solution flow at the beginning stage of the synthesis reaction, the generated cobalt carbonate is prevented from being oxidized by adding a reducing agent hydrazine hydrate, the cobalt carbonate product with the laser particle size of 15-25 mu m can be prepared in a short time, the laser particle size of 15-25 mu m is further prepared, and the tap density is greater than 2.0g/cm3The specific surface area is 1.0-3.0 m2A spherical or spheroidal cobaltosic oxide product per gram.
According to the invention, after the wet synthesis is finished, the cobalt carbonate is oxidized into the cobalt oxyhydroxide by adding hydrogen peroxide into the reaction kettle, so that the step of introducing compressed air or other oxidizing gases in the calcining process is avoided, no dust is generated in the production process, and the method is pollution-free and environment-friendly. And the risk that the impurity content of the lithium cobaltate product exceeds the standard due to the introduction of unclean compressed air or other oxidizing gases is avoided, and the requirement on calcining equipment is relatively simple.
Drawings
FIG. 1 is an SEM photograph of a synthesized product of example 1;
FIG. 2 is an SEM photograph of a synthesized product of example 2;
FIG. 3 is an SEM photograph of a synthesized product of example 3;
FIG. 4 is a process flow diagram of the present invention.
Detailed Description
Example 1
The production steps are the same as above and are not described herein again. The specific parameters in each step are as follows:
the prepared solution A is a 1mol/L cobalt chloride solution.
The prepared solution B is a 1mol/L sodium carbonate solution.
The prepared solution C is 5mol/L ammonia water solution, and 5mL of hydrazine hydrate solution with the mass content of 30% is added in each liter of ammonia water solution.
The prepared solution D is a hydrogen peroxide solution of 5 mol/L.
The prepared solution E is 2mol/L sodium hydroxide solution.
The prepared F solution is a cerium nitrate solution with the concentration of 8.1 g/L.
And (3) synthesis reaction: when the synthesis reaction starts, adding the solution A, the solution B, the solution C and the solution F into a reaction kettle in parallel, and carrying out cobalt carbonate synthesis reaction under strong stirring, wherein the ammonia concentration of the reaction solution is strictly controlled to be 5g/L in the reaction process, the temperature of the reaction system is 70 ℃, the flow rate of the solution A is 100L/h of the flow rate of 0-1 h of the reaction time period, 200L/h of the flow rate of 1-2 h of the time period, 300L/h of the flow rate of 2-3 h of the time period, 400L/h of the flow rate of 3-4 h of the time period, and 500L/h of the flow rate after 4h and until the synthesis reaction is finished, the flow rate of the solution B is 1.02 times of the corresponding flow rate of the solution A in each time period, the flow rate of the solution F is 0.1 time of the corresponding solution A in each time period, the.
And (3) oxidation reaction: after the synthesis is finished, D, E solution is added into the reaction kettle at the same time, cobalt carbonate is oxidized into cobalt oxyhydroxide under strong stirring, the pH value is strictly controlled to be 10.0 in the oxidation process, the reaction temperature is 70 ℃, the oxidation time is 1h, and the usage amount of hydrogen peroxide is 0.5 time of the molar weight of the reaction cobalt.
And after the oxidation process is finished, filtering, slurrying, washing and drying the material to obtain a large-particle-size doped cobaltosic oxide precursor product. The materials are washed by using 80 ℃ deionized water, and the drying temperature of the materials is 200 ℃.
And (3) calcining: the calcining temperature is 700 ℃, the calcining time is 2h, and the large-particle-size doped cobaltosic oxide product is obtained by calcining under the condition of not introducing oxidizing gas.
The indexes of the prepared product are shown in table 1, and the product morphology is shown in figure 1.
TABLE 1 physicochemical indices of the product of example 1
Example 2
The production steps are the same as above and are not described herein again. The specific parameters in each step are as follows:
the prepared solution A is 1.5mol/L cobalt sulfate solution.
The prepared solution B is 1.5mol/L sodium carbonate solution.
The prepared solution C is 8mol/L ammonia water solution, and 15mL of hydrazine hydrate solution with the mass content of 30% is added in each liter of ammonia water solution.
The prepared solution D is 6mol/L hydrogen peroxide solution.
The prepared solution E is 4mol/L sodium hydroxide solution.
The prepared F solution is a magnesium chloride solution with the concentration of 16.2 g/L.
And (3) synthesis reaction: when the synthesis reaction starts, adding the solution A, the solution B and the solution C in a parallel flow manner into a reaction kettle, after 50 hours of the synthesis reaction, adding the solution F into the reaction kettle at a flow rate which is 0.2 times of that of the cobalt sulfate solution, carrying out the cobalt carbonate synthesis reaction under strong stirring, strictly controlling the ammonia concentration of the reaction solution to be 8g/L in the reaction process, controlling the temperature of the reaction system to be 65 ℃, controlling the flow rate of the solution A to be 100L/h in the reaction time period, controlling the flow rate of the solution A to be 200L/h in the time period, controlling the flow rate of the solution A to be 300L/h in the time period, controlling the flow rate of the solution A to be 400L/h in the time period, controlling the flow rate of the solution B to be 1.05 times of the corresponding flow rate of the solution A in each time period, controlling the stirring intensity to be 200 r/min, and controlling the reaction time.
And (3) oxidation reaction: after the synthesis is finished, D, E solution is added into the reaction kettle at the same time, cobalt carbonate is oxidized into cobalt oxyhydroxide under strong stirring, the pH value is controlled to be 10.5 in the oxidation process, the reaction temperature is 65 ℃, the oxidation time is 2 hours, and the usage amount of hydrogen peroxide is 0.6 times of the molar weight of the reacted cobalt.
And after the oxidation process is finished, filtering, slurrying, washing and drying the material to obtain a large-particle-size doped cobaltosic oxide precursor product. The material washing is carried out by using deionized water at 90 ℃, and the material drying temperature is 300 ℃.
And (3) calcining: the calcining temperature is 750 ℃, the calcining time is 5h, and the large-particle-size doped cobaltosic oxide product is obtained by calcining under the condition of not introducing oxidizing gas.
The indexes of the prepared product are shown in Table 2, and the product morphology is shown in figure 2.
TABLE 2 physicochemical indices of the product of example 2
Example 3
The production steps are the same as above and are not described herein again. The specific parameters in each step are as follows:
the prepared solution A is a 2mol/L cobalt nitrate solution.
The prepared solution B is 2mol/L sodium carbonate solution.
The prepared solution C is 10mol/L ammonia water solution, and 20mL of hydrazine hydrate solution with the mass content of 30% is added in each liter of ammonia water solution.
The prepared solution D is 8mol/L hydrogen peroxide solution.
The prepared solution E is 6mol/L sodium hydroxide solution.
The prepared F solution is 48.6g/L of aluminum trichloride solution.
And (3) synthesis reaction: when the synthesis reaction starts, adding the solution A, the solution B and the solution C into a reaction kettle in a cocurrent manner, carrying out cobalt carbonate synthesis reaction under the condition of strong stirring, after the synthesis is finished, adding the solution F into a reaction kettle at a cobalt nitrate solution flow rate for reaction for 1h, controlling the ammonia concentration of the reaction solution to be 6g/L in the reaction process, controlling the temperature of a reaction system to be 75 ℃, controlling the flow rate of the solution A to be 100L/h in the reaction time period, controlling the flow rate of the solution A to be 200L/h in the reaction time period, controlling the flow rate of the solution B to be 300L/h in the reaction time period, controlling the flow rate of the solution A to be 400L/h in the reaction time period, controlling the flow rate of the solution A to be 4 h-500L/h in the reaction time period, controlling the flow rate of the solution B to be 1.1 times of the corresponding flow rate of the solution A in each time period, controlling the stirring intensity to be 500 r/min and.
And (3) oxidation reaction: after the synthesis is finished, D, E solution is added into the reaction kettle at the same time, cobalt carbonate is oxidized into cobalt oxyhydroxide under strong stirring, the pH value is controlled to be 11 in the oxidation process, the reaction temperature is 75 ℃, the oxidation time is 2 hours, and the usage amount of hydrogen peroxide is 0.55 times of the molar weight of the reaction cobalt.
And after the oxidation process is finished, filtering, slurrying, washing and drying the material to obtain a large-particle-size doped cobaltosic oxide precursor product. Deionized water at 90 ℃ is adopted for washing materials, and the temperature condition for drying the materials is 400 ℃.
And (3) calcining: the calcination temperature is 780 ℃, the calcination time is 4h, and the product of large-particle-size doped cobaltosic oxide is obtained by calcination without introducing oxidizing gas.
The indexes of the prepared product are shown in Table 3, and the product appearance diagram is shown in figure 3.
TABLE 3 physicochemical indices of the product of example 3
Claims (6)
1. A preparation method of large-particle-size doped cobaltosic oxide is characterized by comprising the following specific steps:
a. preparing solution A
Preparing a cobalt solution with the cobalt concentration of 1-2 mol/L as an A solution by using cobalt salt as a raw material;
b. preparing solution B
Preparing a sodium carbonate solution with the concentration of 1-2 mol/L as a B solution, wherein the molar concentration of sodium carbonate in the B solution is the same as that of cobalt in the A solution;
c. preparing solution C
Preparing an ammonia water solution with the concentration of 5-10 mol/L, and adding 5-20 ml of hydrazine hydrate solution with the mass content of 30% into each liter of ammonia water solution to obtain a solution C;
d. preparing solution D
Preparing a hydrogen peroxide solution with the concentration of 5-10 mol/L as a solution D;
e. preparation of solution E
Preparing a sodium hydroxide solution with the concentration of 2-6 mol/L as an E solution;
f. preparing solution F
Preparing a doping element soluble salt solution with the concentration of 5-50 g/L to be an F solution;
g. synthesis reaction
When the synthesis reaction starts, the solution A, the solution B and the solution C are added into a reaction kettle in parallel, adding the F solution into a reaction kettle for a proper time according to the chemical properties of the doped element compound, carrying out cobalt carbonate synthesis reaction under stirring, wherein the ammonia concentration of a solution in a reaction kettle is strictly controlled to be 5-10 g/L, the reaction temperature is 60-80 ℃, the flow rate of the solution A is 0-1 h of 100L/h in the reaction time period, the flow rate of the solution A is 1-2 h of 200L/h in the reaction time period, the flow rate of the solution A is 300L/h in the reaction time period, the flow rate of the solution A is 400L/h in the reaction time period, the flow rate of the solution B is 1.0-1.1 times of the flow rate of the solution A in the synthesis reaction process after 4h until the synthesis reaction is finished, the stirring intensity is 200-500 r/min, and the reaction time is 10-15 h;
h. oxidation by oxygen
After the synthesis is finished, simultaneously adding D, E solution into a reaction kettle, oxidizing cobalt carbonate precipitate into cobalt oxyhydroxide under stirring, and strictly controlling the pH value, the reaction temperature and the oxidation time in the oxidation process;
i. filtering, washing and drying
After the oxidation process is finished, filtering, slurrying, washing and drying the material to obtain a large-particle-size doped cobaltosic oxide precursor product;
j. calcination of
And (e) calcining the product obtained in the step (i) under a certain condition to obtain a large-particle-size doped cobaltosic oxide product.
2. The method for preparing large-particle-size doped cobaltosic oxide according to claim 1, wherein the method comprises the following steps: in the step a, the cobalt salt is one or more of cobalt sulfate, cobalt nitrate or cobalt chloride.
3. The method for preparing large-particle-size doped cobaltosic oxide according to claim 1, wherein the method comprises the following steps: in the step f, the doping element soluble salt is one or more chlorides or nitrates of Ni, Mn, Al, Cu, Ce, Y, Nb and Mg.
4. The method for preparing large-particle-size doped cobaltosic oxide according to claim 1, wherein the method comprises the following steps: in the oxidation process, the pH value, the reaction temperature and the oxidation time are strictly controlled to be 10-11, the reaction temperature is 60-80 ℃, and the oxidation time is 1-2 hours.
5. The method for preparing large-particle-size doped cobaltosic oxide according to claim 1, wherein the method comprises the following steps: in the step i, deionized water at 80-100 ℃ is adopted for slurrying and washing the materials, and the drying temperature of the materials is 100-400 ℃.
6. The method for preparing large-particle-size doped cobaltosic oxide according to claim 1, wherein the method comprises the following steps: in the step j, the calcining condition is that the calcining temperature is 700-800 ℃ and the calcining time is 2-5 h under the condition of not introducing oxidizing gas.
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