CN115321605A - Preparation method and application of crystal-transition aluminum-doped cobalt carbonate - Google Patents

Preparation method and application of crystal-transition aluminum-doped cobalt carbonate Download PDF

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CN115321605A
CN115321605A CN202211005331.5A CN202211005331A CN115321605A CN 115321605 A CN115321605 A CN 115321605A CN 202211005331 A CN202211005331 A CN 202211005331A CN 115321605 A CN115321605 A CN 115321605A
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ammonium bicarbonate
crystal
aluminum
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CN115321605B (en
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卢星华
李长东
阮丁山
刘更好
周思源
王永平
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Guangdong Brunp Recycling Technology Co Ltd
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Abstract

The invention discloses a preparation method of crystal transformation aluminum-doped cobalt carbonate, which comprises the following steps: (1) Preparing a cobalt salt and an aluminum salt into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution; (2) Adding the mixed metal solution and the second ammonium bicarbonate solution into the first ammonium bicarbonate solution in a concurrent flow manner for reaction, and controlling the reaction temperature to be 40-45 ℃ until the specific surface area is 0.3-0.6cm 2 Crystal transformation and aluminum-doped cobalt carbonate crystal seeds per gram; (3) Adding a mixed metal solution and a third ammonium bicarbonate solution into the solution containing the crystal-transition aluminum-doped cobalt carbonate crystal seeds obtained in the step (2) in a parallel flow manner for mixing and reacting until the granularity of the crystal-transition aluminum-doped cobalt carbonate crystal seeds grows to 16.0-19.0 mu m, carrying out solid-liquid separation, washing and drying the obtained solid to obtain crystal-transition aluminum-doped cobalt carbonateAnd (4) cobalt acid. The crystal-transition aluminum-doped cobalt carbonate prepared by the preparation method has a good aluminum-doped effect.

Description

Preparation method and application of crystal-transition aluminum-doped cobalt carbonate
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method and application of crystal-transition aluminum-doped cobalt carbonate.
Background
The lithium cobaltate cathode material is mainly applied to the 3C field due to the advantage of high energy density. High voltage lithium cobaltate can have higher capacity, but the structure is easy to collapse during the cycle process, and in order to improve the cycle performance, a certain amount of aluminum element is usually doped in the cobaltosic oxide precursor.
In the preparation process of the aluminum-doped cobalt carbonate, the aluminum may exist in the form of amorphous aluminum carbonate, crystal aluminum hydroxide or crystal basic ammonium aluminum carbonate and other compounds. In order to ensure the uniformity of aluminum doping, the reaction conditions are usually controlled, and aluminum is doped into the cobalt carbonate particles in the form of amorphous aluminum carbonate, but the substances are extremely unstable and are easy to hydrolyze and recrystallize in the washing and drying processes of products, so that the aluminum doping effect is poor, aluminum segregation occurs, and the cycle performance of the aluminum-doped cobalt carbonate is affected.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a preparation method and application of crystal-transformation aluminum-doped cobalt carbonate, and the crystal-transformation aluminum-doped cobalt carbonate prepared by the preparation method of crystal-transformation aluminum-doped cobalt carbonate has a good aluminum-doping effect, so that the aluminum-doped cobalt carbonate is ensured to have good cycle performance.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of crystal-transition aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a mixed metal solution from cobalt salt and aluminum salt, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of the first ammonium bicarbonate solution is 0.8-1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5-3.0mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5-2.0mol/L;
(2) Adding the mixed metal solution and the second ammonium bicarbonate solution into the first ammonium bicarbonate solution in a concurrent flow manner for reaction, and controlling the reaction temperature to be 40-45 ℃ until the specific surface area is 0.3-0.6cm 2 Crystal transformation and aluminum-doped cobalt carbonate crystal seeds per gram;
(3) And (3) adding the mixed metal solution and the third ammonium bicarbonate solution into the solution containing the crystal-transformation aluminum-doped cobalt carbonate crystal seeds obtained in the step (2) in a parallel flow manner, mixing and reacting until the granularity of the crystal-transformation aluminum-doped cobalt carbonate crystal seeds grows to 16.0-19.0 mu m, carrying out solid-liquid separation, washing and drying the obtained solid, and obtaining the crystal-transformation aluminum-doped cobalt carbonate.
Preferably, in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5 to 2.5mol/L, and the molar ratio of the aluminum element to the cobalt element is 0.001 to 0.01.
Further preferably, in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5 to 2.2mol/L, and the molar ratio of the aluminum element to the cobalt element is 0.005 to 0.01.
Preferably, in the step (1), the cobalt salt is at least one of cobalt sulfate, cobalt nitrate or cobalt chloride.
Preferably, in the step (1), the aluminum salt is at least one of aluminum sulfate, aluminum chloride or aluminum nitrate.
Preferably, the reactions in the step (2) and the step (3) are performed in a reaction kettle, in the step (2), the first ammonium bicarbonate solution is added into the reaction kettle as a base solution and heated, the mixed metal solution and the second ammonium bicarbonate solution are added into the reaction kettle in a parallel flow manner through a liquid adding pipe under a stirring state for reaction, when the liquid level in the reaction kettle reaches a set value, concentration is started, and the specific surface area of the generated seed crystal is monitored until the specific surface area of the seed crystal reaches a target value.
Preferably, in the step (2), the base solution accounts for 20% -30% of the total volume of the reaction kettle, the flow rate of the mixed metal solution is 200-300L/h, the flow rate of the second ammonium bicarbonate solution is 100-150L/h, when the liquid level in the reaction kettle reaches 80% -85% of the total volume of the reaction kettle, concentration is started, and the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced to stabilize the liquid level in the kettle at 80% -85% of the total volume.
Preferably, the pH of the reaction in step (2) is controlled to be 7.0 to 8.5.
It is further preferred that the pH of the reaction in the step (2) is controlled to 7.0 to 7.5.
Preferably, in the step (3), the mixed metal solution and the third ammonium bicarbonate solution are added in parallel through a liquid adding pipe on the premise of starting concentration, the flow rate of the mixed metal solution is 100-200L/h, the pH of the reaction is controlled to be 7.8-8.2 by continuously adding the third ammonium bicarbonate solution, the liquid level in the kettle is stabilized to be 80% -85% of the total volume, and the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same. Preferably, in the step (3), the reaction temperature is increased to 60-80 ℃ at a temperature increasing rate of 10-30 ℃/h.
Further preferably, in the step (3), the reaction temperature is raised to 65 to 70 ℃ at a temperature raising rate of 20 to 30 ℃/h.
Preferably, the number of the liquid adding pipes of the mixed metal solution in the step (3) is more than that of the liquid adding pipes of the mixed metal solution in the step (2), and the number of the liquid adding pipes of the third ammonium bicarbonate solution in the step (3) is more than that of the liquid adding pipes of the second ammonium bicarbonate solution in the step (2).
Preferably, the number of the liquid adding pipes of the mixed metal solution and the second ammonium bicarbonate solution in the step (2) is one.
Preferably, the obtained material is further sieved and packaged after being dried in the step (3).
Preferably, the mesh size is 300-500 mesh, for example 400 mesh.
Preferably, the temperature of the water used for washing in the step (3) is 60-100 ℃, and the washing time is 20-100min.
Further preferably, the temperature of the water used for washing in the step (3) is 80-100 ℃, and the washing time is 30-60min.
Preferably, the drying temperature in the step (3) is 100-150 ℃, and the moisture in the dried material is less than 5%.
Further preferably, the drying temperature in the step (3) is 120-130 ℃, and the moisture in the dried material is lower than 1%.
The crystal-transition aluminum-doped cobalt carbonate prepared by the preparation method is applied to preparation of a lithium cobaltate positive electrode material.
The invention has the beneficial effects that:
(1) The invention keeps the lower temperature of 40-45 ℃ during the crystal seed synthesis, can slow down the precipitation speed of aluminum, and leads the aluminum to be doped in the cobalt carbonate in the form of amorphous aluminum carbonate, thus being beneficial to the uniform distribution of the aluminum; simultaneously preparing 0.3-0.6cm 2 The aluminum-doped cobalt carbonate particles with low specific surface area/g are used as crystal transformation cobalt carbonate crystal seeds, the surfaces of the crystal transformation cobalt carbonate crystal seeds have rich surface defects, mountain-peak-shaped primary particles are more prominent, gaps among the primary particles are larger, sufficient growth sites are provided for secondary nucleation of flaky crystal cobalt carbonate, the flaky crystal is enabled to stably grow in the gaps and gradually cover the surfaces of the whole particles, and the purpose of cobalt carbonate crystal transformation is achieved; if the specific surface area of the seed crystal is larger, the defects on the surface of the particle are less, the arrangement of the mountain peak-shaped primary particles is dense, the gaps among the primary particles are smaller, the surface of the particle is smoother, the flaky crystal form is difficult to stably grow, and the newly generated cobalt carbonate crystal grains tend to grow on the original mountain peak-shaped primary particles, so that the aim of completely converting the cobalt carbonate crystal form is difficult to achieve.
(2) The single metal liquid adding pipe and the single ammonium bicarbonate solution liquid adding pipe are used during the preparation of the seed crystal, so that the supersaturation degree at the feeding moment can be increased, and more crystal nuclei are generated; and the quantity of liquid feeding pipes of the metal liquid and the ammonium bicarbonate solution is respectively increased in the processes of cobalt carbonate crystal form conversion and growth, so that the instantaneous supersaturation degree of feeding can be reduced under the condition of unchanging total liquid feeding amount, the generation of small particles is avoided, and the decomposition of the ammonium bicarbonate solution can be accelerated.
(3) In the invention, aluminum is doped in cobalt carbonate in the form of amorphous aluminum carbonate during the synthesis of crystal seeds, and ammonium bicarbonate is decomposed into more hydroxide ions by using higher synthesis temperature, higher heating rate, lower ammonium bicarbonate solution concentration and a plurality of ammonium bicarbonate solution liquid adding pipes at the stage of cobalt carbonate crystal form conversion and growth, so that the hydroxide ion concentration in a reaction system is quickly increased, the carbonate ion concentration is reduced, each ion concentration of the synthesis system is mutated, sufficient driving force is provided for crystal conversion, the newly generated aluminum-doped cobalt carbonate crystal form is converted, and the converted flaky crystal form of basic cobalt aluminum carbonate grows on the crystal seeds with abundant surface defects in a standing and stacking manner; if the temperature rise speed is slow and the temperature is not raised to a certain range or the ammonium bicarbonate concentration is high during the regulation and control of the cobalt carbonate crystal form transition period, namely the carbonate ion concentration in the system is high, basic cobalt aluminum carbonate is difficult to generate, and obvious crystal form mutation cannot occur; by maintaining a higher reaction pH value, the phase components of the basic cobalt aluminum carbonate can be further increased, the aim of completely transforming the crystal of the aluminum-doped cobalt carbonate is fulfilled, and the crystal transformation process is irreversible; from the formula: 6CoCl 2 +Al 2 (SO 4 ) 3 +20H 2 O+18NH 4 HCO 3 ＝Co 6 Al 2 CO 3 (OH) 16 ·4H 2 O↓+3(NH 4 ) 2 SO 4 +12NH 4 Cl+17H 2 CO 3 The basic cobalt aluminum carbonate can be used for stably coprecipitating aluminum ions and cobalt ions, so that the aluminum is easier to dope in the crystal lattices of the cobalt carbonate, the distribution uniformity of the aluminum can be improved, the crystallized product is more stable, the subsequent process is convenient and more beneficial to the embedding of lithium, the battery has better cycle performance, the reaction rate can be accelerated by synthesis at high temperature, the precipitation rate of the cobalt is improved, the cobalt content in the mother solution is stabilized below 50ppm, and the wastewater treatment cost is saved.
Drawings
FIG. 1 is a SEM image of a crystal-transferred aluminum-doped cobalt carbonate seed crystal in example 1 of the present invention;
FIG. 2 is a SEM image of a crystal-converted aluminum-doped cobalt carbonate finished product in example 1 of the present invention;
FIG. 3 is an XRD pattern of the crystal-transition aluminum-doped cobalt carbonate finished product in example 1 of the present invention;
FIG. 4 is a SEM image of a crystal-transferred aluminum-doped cobalt carbonate seed crystal in example 2 of the present invention;
FIG. 5 is a SEM image of a crystal-transferred aluminum-doped cobalt carbonate finished product in example 2 of the present invention;
FIG. 6 is an SEM image of a crystal-transferred aluminum-doped cobalt carbonate finished product in example 3 of the present invention;
FIG. 7 is an SEM image of a finished cobalt aluminum-doped carbonate of comparative example 1 in accordance with the present invention;
FIG. 8 is an SEM image of an aluminum-doped cobalt carbonate seed of comparative example 2 in accordance with the present invention;
FIG. 9 is an SEM image of a finished product of comparative example 2 aluminum-doped cobalt carbonate of the present invention;
FIG. 10 is an SEM image of a finished product of comparative example 3 aluminum-doped cobalt carbonate of the present invention;
FIG. 11 is an SEM image of a finished product of comparative example 4 aluminum-doped cobalt carbonate of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of crystal-transition aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt chloride and aluminum chloride into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.0mol/L, the molar ratio of aluminum to cobalt is 0.01, the concentration of the first ammonium bicarbonate solution is 1.0mol/L, the concentration of the second ammonium bicarbonate solution is 3mol/L, and the concentration of the third ammonium bicarbonate solution is 2mol/L;
(2) Crystal transformation cobalt carbonate seed crystal synthesis: adding a first ammonium bicarbonate solution into a reaction kettle as a base solution, wherein the volume of the first ammonium bicarbonate solution accounts for 30% of the total volume of the reaction kettle, the pH value of the base solution is 8.3, starting to heat to 45 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; wherein the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipeSimultaneously feeding liquid, wherein the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is adjusted by a PLC control system to stabilize the pH value to be 7.50, when the liquid level in the reaction kettle reaches 83% of the total volume, concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced during concentration, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, and when the BET measured by a seed crystal sample is 0.35cm 2 The synthesis of the crystal seed of the crystal-transformed aluminum-doped cobalt carbonate is finished at the time of/g, the SEM image of the obtained crystal seed of the crystal-transformed aluminum-doped cobalt carbonate is shown in figure 1, the D50 is measured to be 8.6 mu m, and meanwhile, the primary particles are blocky and have no aluminum segregant according to figure 1;
(3) And (3) cobalt carbonate crystal transformation and growth: raising the reaction temperature to 65 ℃, controlling the temperature rise speed of the reaction kettle to be 20 ℃/h, adding the mixed metal solution and the third ammonium bicarbonate solution in a parallel flow manner, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are both three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used by the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is adjusted by a PLC control system, the pH value of the seed crystal growth stage is constantly 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously introduced during the concentration period, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, the concentration of cobalt ions in the mother solution is 40mg/L during the reaction process, and when the particle size grows to be 16.7 mu m, the crystal-transformed aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving crystal transformation aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing the slurry by hot pure water at 85 ℃ for 40min, drying a filter cake at 110 ℃ until the moisture content is 0.1%, sieving the filter cake by a 400-mesh vibrating screen, and packaging to obtain a crystal-converted aluminum-doped cobalt carbonate finished product, wherein an SEM picture of the obtained crystal-converted aluminum-doped cobalt carbonate finished product is shown in figure 2, an XRD picture of the obtained crystal-converted aluminum-doped cobalt carbonate finished product is shown in figure 3, wherein D50 is 16.7 mu m, the aluminum element content is 4820ppm, as can be seen from figure 2, primary particles are flaky and have no aluminum segregation, as can be seen from figure 3, the obtained crystal-converted aluminum-doped cobalt carbonate finished product is a mixture of cobalt carbonate and basic cobalt aluminum carbonate.
Example 2:
a preparation method of crystal-transition aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt sulfate and aluminum sulfate into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.2mol/L, the molar ratio of aluminum and cobalt elements is 0.008, the concentration of the first ammonium bicarbonate solution is 0.8mol/L, the concentration of the second ammonium bicarbonate solution is 2.8mol/L, and the concentration of the third ammonium bicarbonate solution is 1.7mol/L;
(2) Crystal transformation cobalt carbonate seed crystal synthesis: adding a first ammonium bicarbonate solution into a reaction kettle as a base solution, wherein the volume of the first ammonium bicarbonate solution is 40 percent of the total volume of the reaction kettle, the pH value of the base solution is 7.5, starting to heat to 43 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes which are used for simultaneously feeding liquid, the flow rate of the mixed metal solution is 250L/h, the flow rate of the second ammonium bicarbonate solution is 120L/h, when the pH value is reduced to 7.40, the flow rate of the second ammonium bicarbonate solution is adjusted through a PLC control system so as to stabilize the pH value to be 7.40, when the liquid level in the reaction kettle reaches 80% of the total volume, concentration is started, the mixed metal solution and the ammonium bicarbonate A solution are continuously introduced during concentration, the liquid level in the kettle is kept to be stabilized at 80% of the total volume, and when the BET measured by a seed crystal sample is 0.41cm 2 The synthesis of the crystal seed of the crystal-transformed aluminum-doped cobalt carbonate is finished at the time of/g, the SEM image of the obtained crystal seed of the crystal-transformed aluminum-doped cobalt carbonate is shown in figure 4, the D50 is measured to be 10.5 mu m, and as can be seen from figure 4, the primary particles are blocky and have no aluminum segregants;
(3) And (3) cobalt carbonate crystal transformation and growth: raising the reaction temperature to 67 ℃, controlling the temperature rise speed of the reaction kettle to be 24 ℃/h, adding the mixed metal solution and the third ammonium bicarbonate solution in a concurrent flow manner, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are all four liquid adding pipes for feeding liquid simultaneously, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 250L/h, the flow rate of the third ammonium bicarbonate solution is adjusted through a PLC (programmable logic controller) control system, the pH value of the seed crystal growth stage is constantly 8.2, the mixed metal solution and the third ammonium bicarbonate solution are continuously introduced during the concentration period, the liquid level in the kettle is kept stable at 80% of the total volume, the concentration of cobalt ions in the mother liquor is 20mg/L during the reaction process, and when the particle size grows to be 18.8 mu m, so as to obtain the crystal-transformed aluminum-doped cobalt carbonate slurry;
(4) Washing, drying and sieving crystal transformation aluminum-doped cobalt carbonate: and filtering the slurry in the reaction kettle by using a centrifugal machine, washing the slurry by using hot pure water at 90 ℃ for 30min, drying a filter cake at 120 ℃ until the moisture content is 0.28%, sieving the filter cake by using a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM image of the obtained crystal-transition aluminum-doped cobalt carbonate finished product is shown in figure 5, wherein D50 is 18.8 mu m, the aluminum element content is 3693ppm, and as can be seen from figure 5, primary particles are flaky and do not contain aluminum segregation.
Example 3:
a preparation method of crystal-transition aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt nitrate and aluminum nitrate into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 1.5mol/L, the molar ratio of aluminum to cobalt is 0.005, the concentration of the first ammonium bicarbonate solution is 1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5mol/L;
(2) Crystal transformation cobalt carbonate seed crystal synthesis: adding a first ammonium bicarbonate solution into a reaction kettle as a base solution, wherein the volume of the first ammonium bicarbonate solution accounts for 35% of the total volume of the reaction kettle, the pH value of the base solution is 8.5, starting to heat to 40 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes which are used for simultaneously feeding liquid, the flow rate of the mixed metal solution is 200L/h, the flow rate of the second ammonium bicarbonate solution is 100L/h, when the pH value is reduced to 7.60, the flow rate of the second ammonium bicarbonate solution is adjusted through a PLC control system so as to stabilize the pH value to be 7.60 constantly, when the liquid level in the reaction kettle reaches 85% of the total volume, concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced during concentration, the liquid level in the kettle is kept to be 85% of the total volume, and when the BET measured by a seed crystal sample is 0.56cm 2 At a time of/gThe crystal transformation aluminum-doped cobalt carbonate crystal seed synthesis is completed, the D50 is measured to be 12.5 mu m, the primary particles are blocky, and no aluminum segregation is generated;
(3) And (3) cobalt carbonate crystal transformation and growth: raising the reaction temperature to 70 ℃, controlling the temperature rise speed of the reaction kettle to be 30 ℃/h, adding a mixed metal solution and a third ammonium bicarbonate solution in a parallel flow manner, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are both two liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used by the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 100L/h, the flow rate of the third ammonium bicarbonate solution is adjusted through a PLC control system, the pH value of the seed crystal growth stage is constantly 7.8, the mixed metal solution and the third ammonium bicarbonate solution are continuously introduced during the concentration period, the liquid level in the kettle is kept to be stabilized at 85% of the total volume, the concentration of cobalt ions in the mother liquor in the reaction process is 50mg/L, and when the particle size grows to be 17.5 mu m, the crystal-transformed aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving crystal transformation aluminum-doped cobalt carbonate: and filtering the slurry in the reaction kettle by a centrifugal machine, washing the slurry by hot pure water at 95 ℃ for 600min, drying a filter cake at 110 ℃ until the moisture content is 0.82%, screening the filter cake by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM image of the obtained crystal-transition aluminum-doped cobalt carbonate finished product is shown in figure 6, wherein D50 is 17.5 mu m, the aluminum element content is 2420ppm, and as can be seen from figure 6, primary particles are flaky and do not contain aluminum segregation.
Comparative example 1:
a preparation method of aluminum-doped cobalt carbonate comprises the following steps:
(1) Same as in step (1) of example 1;
(2) And (3) synthesizing aluminum-doped cobalt carbonate seed crystal: same as in step (2) of example 1;
(3) Growing aluminum-doped cobalt carbonate: controlling the reaction temperature to be constant at 45 ℃, keeping the temperature the same as that of a seed crystal, adding a mixed metal solution and a third ammonium bicarbonate solution in parallel, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are both three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC (programmable logic controller) control system, the pH value of the seed crystal growth stage is constantly 7.50 and is the same as that controlled by the seed crystal reaction, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in during the concentration period, the liquid level in a kettle is kept to be stable at 83% of the total volume, the concentration of cobalt ions in a mother solution is 150mg/L in the reaction process, and when the particle size grows to 16.6 mu m, so as to obtain the aluminum-doped cobalt carbonate slurry;
(4) Washing, drying and sieving the aluminum-doped cobalt carbonate: and filtering the slurry in the reaction kettle by a centrifugal machine, washing the slurry by hot pure water at 85 ℃ for 40min, drying a filter cake at 110 ℃ until the moisture content is 0.21%, sieving the filter cake by a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein the SEM image of the obtained aluminum-doped cobalt carbonate finished product is shown in figure 7, the D50 is 16.6 mu m, the aluminum element content is 4758ppm, and as can be seen from figure 7, the primary particles are blocky, crystal transformation does not occur, and aluminum sheets are separated out on the surface.
Comparative example 2:
a preparation method of aluminum-doped cobalt carbonate comprises the following steps:
(1) Same as in step (1) of example 1;
(2) And (3) synthesizing aluminum-doped cobalt carbonate seed crystal: adding a first ammonium bicarbonate solution into a reaction kettle as a base solution, wherein the volume of the first ammonium bicarbonate solution accounts for 30% of the total volume of the reaction kettle, the pH value of the base solution is 8.3, starting to heat to 43 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in parallel under the condition of high-speed stirring; the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes and simultaneously feed liquid, the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is adjusted through a PLC control system to stabilize the pH value to be 7.50, when the liquid level in the reaction kettle reaches 83% of the total volume, concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced during concentration, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, and when the BET measured by a seed crystal sample is 5.2cm 2 The synthesis of the aluminum-doped cobalt carbonate seed crystal is finished at the time of/g, the SEM image of the obtained aluminum-doped cobalt carbonate seed crystal is shown in figure 8, the D50 is measured to be 6.2 mu m, and as can be seen from figure 8, the primary particles are small blocks without obvious aluminumA segregant;
(3) Growing aluminum-doped cobalt carbonate: same as in step (3) of example 1;
(4) Washing, drying and sieving the aluminum-doped cobalt carbonate: and filtering the slurry in the reaction kettle by using a centrifugal machine, washing the slurry by using hot pure water at 85 ℃ for 40min, drying a filter cake at 110 ℃ until the moisture content is 0.15%, sieving the filter cake by using a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein an SEM picture of the obtained aluminum-doped cobalt carbonate finished product is shown in figure 9, wherein D50 is 16.5 mu m, the aluminum element content is 4810ppm, and as can be seen from figure 9, primary particles are in a large block shape and have obvious aluminum segregation.
Comparative example 3:
a preparation method of aluminum-doped cobalt carbonate comprises the following steps:
(1) Same as in step (1) of example 1;
(2) Same as in step (2) of example 1;
(3) Growing aluminum-doped cobalt carbonate: raising the reaction temperature to 50 ℃, controlling the temperature raising speed to be 5 ℃/h, adding the mixed metal solution and the third ammonium bicarbonate solution in a concurrent flow manner, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are both three liquid adding pipes for simultaneously feeding liquid, the sizes of the liquid adding pipes used by the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC control system, the pH value of the seed crystal growth stage is constantly 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in during concentration, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, the concentration of cobalt ions in mother liquor in the reaction process is 150mg/L, and when the particle size grows to 16.7 mu m, the aluminum-doped cobalt carbonate slurry is obtained;
(4) Washing, drying and sieving the aluminum-doped cobalt carbonate: filtering the slurry in the reaction kettle by a centrifugal machine, washing with hot pure water at 85 ℃ for 40min, drying a filter cake at 120 ℃ until the moisture content is 0.28%, sieving with a 400-mesh vibrating screen, and packaging to obtain an aluminum-doped cobalt carbonate finished product, wherein the SEM image of the obtained aluminum-doped cobalt carbonate finished product is shown in figure 10, the D50 is 16.9 mu m, the aluminum element content is 4729ppm, and as can be seen from figure 10, the primary particles are of a mixed crystal form of blocks and sheets, and have obvious aluminum segregation and are inserted on the surfaces of the particles.
Comparative example 4:
a preparation method of aluminum-doped cobalt carbonate comprises the following steps:
(1) Preparing a solution: preparing cobalt chloride and aluminum chloride into mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of cobalt in the mixed metal solution is 2.0mol/L, the molar ratio of aluminum to cobalt is 0.01, the concentration of the first ammonium bicarbonate solution is 1.0mol/L, and the concentrations of the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are both 3mol/L;
(2) Crystal transformation cobalt carbonate seed crystal synthesis: adding a first ammonium bicarbonate solution serving as a base solution into a reaction kettle, wherein the volume of the first ammonium bicarbonate solution is 30 percent of the total volume of the reaction kettle, the pH value of the base solution is 8.3, heating to 45 ℃, and adding a mixed metal solution and a second ammonium bicarbonate solution in a concurrent flow manner under the condition of high-speed stirring; the mixed metal solution and the second ammonium bicarbonate solution are both single liquid adding pipes which are used for simultaneously feeding liquid, the flow rate of the mixed metal solution is 300L/h, the flow rate of the second ammonium bicarbonate solution is 150L/h, when the pH value is reduced to 7.50, the flow rate of the second ammonium bicarbonate solution is adjusted through a PLC control system so as to stabilize the pH value to be 7.50 constantly, when the liquid level in the reaction kettle reaches 83% of the total volume, concentration is started, the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced during concentration, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, and when the BET measured by a seed crystal sample is 0.30cm 2 Completing the synthesis of crystal-transition aluminum-doped cobalt carbonate crystal seeds at the time of/g;
(3) And (3) cobalt carbonate crystal transformation and growth: raising the reaction temperature to 65 ℃, controlling the temperature rise speed of the reaction kettle to be 20 ℃/h, adding the mixed metal solution and the third ammonium bicarbonate solution in a concurrent flow manner, starting concentration, wherein the mixed metal solution and the third ammonium bicarbonate solution are simultaneously fed by a single liquid feeding pipe, the sizes of the liquid feeding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same, the flow rate of the mixed metal solution is 200L/h, the third ammonium bicarbonate solution is regulated by a PLC (programmable logic controller) control system, the pH value of the seed crystal growth stage is constantly 8.0, the mixed metal solution and the third ammonium bicarbonate solution are continuously fed in during concentration, the liquid level in the kettle is kept to be stabilized at 83% of the total volume, the concentration of cobalt ions in the mother solution is 40mg/L during the reaction process, and when the particle size grows to be 16.7 mu m, so as to obtain the aluminum-doped cobalt carbonate slurry;
(4) Washing, drying and sieving crystal transformation aluminum-doped cobalt carbonate: and filtering the slurry in the reaction kettle by using a centrifugal machine, washing the slurry by using hot pure water at 85 ℃ for 40min, drying a filter cake at 110 ℃ until the moisture content is 0.5%, sieving the filter cake by using a 400-mesh vibrating screen, and packaging to obtain a crystal-converted aluminum-doped cobalt carbonate finished product, wherein an SEM picture of the obtained aluminum-doped cobalt carbonate finished product is shown in a figure 11, wherein D50 is 16.7 mu m, the aluminum element content is 4810ppm, and as can be seen from the figure 11, the primary particles are blocky, crystal conversion does not occur, and aluminum segregation is cut on the surfaces of the particles.
By comparing the example 1 with the comparative example 1, the basic cobalt aluminum carbonate with the flaky morphology formed after crystal transformation not only ensures the uniformity of aluminum distribution in the synthesis process, but also avoids the precipitation of aluminum sheets in the post-treatment process of finished products due to the structural stability; by comparing the example 1 with the comparative example 2, the crystal seeds with larger specific surface area can not be subjected to crystal transformation under the growth conditions of high temperature and high pH, and the primary particles still inherit the blocky appearance of the crystal seeds and become larger along with the growth of the particles; by comparing the example 1 with the comparative example 3, in the crystal form conversion and growth stage of the cobalt carbonate, the temperature rise rate is slow, the temperature is low, the grains can not be completely transformed, the primary grains are in coarse block and flake adhesion, and the consistency of the surfaces of the grains is poor; by comparing the example 1 with the comparative example 4, it can be shown that the ammonium bicarbonate concentration and the single liquid adding pipe liquid adding mode which are the same as those in the seed crystal preparation stage are adopted in the crystal form conversion and growth stage of the aluminum-doped cobalt carbonate, the carbonate ion concentration in the mother liquid is still kept at a high value, and the grain crystal transformation can not occur.
The cobalt carbonate precursors prepared in examples 1-3 and comparative examples 1-4 above were calcined in a chamber furnace at 700 ℃ for 4 hours, and then prepared into batteries under the same conditions for electrochemical testing, by the approximate method: a lithium cobaltate material prepared by mixing and sintering a precursor and lithium carbonate according to a certain proportion is used as a positive electrode, graphite is used as a negative electrode, lithium hexafluorophosphate is used as electrolyte to prepare a button cell, the electrochemical test voltage is 4.55V, a 1C high-temperature cycle test is carried out, the temperature is 45 ℃, and the test result is shown in the following table 1:
table 1: and (3) testing the cycle performance of the battery:
item Cycle retention at 50 weeks Cycle retention at 80 weeks
Example 1 92.5％ 83.1％
Example 2 91.8％ 82.7％
Example 3 90.6％ 81.5％
Comparative example 1 85.1％ 72.5％
Comparative example 2 82.5％ 73.6％
Comparative example 3 82.4％ 70.8％
Comparative example 4 84.6％ 71.3％
As can be seen from the data in table 1, the aluminum-doped precursor after crystal transformation prepared in each example is more favorable for lithium intercalation after being prepared into lithium cobaltate, and has excellent cycle performance, the cycle retention rate of 50 cycles can reach more than 90.6%, and the cycle retention rate of 80 cycles can reach more than 81.5%, while the aluminum-doped precursor without crystal transformation prepared in the comparative example has uneven aluminum distribution, which results in poor high-temperature cycle performance of the lithium cobaltate material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A preparation method of crystal-transformation aluminum-doped cobalt carbonate is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a cobalt salt and an aluminum salt into a mixed metal solution, and preparing a first ammonium bicarbonate solution, a second ammonium bicarbonate solution and a third ammonium bicarbonate solution, wherein the concentration of the first ammonium bicarbonate solution is 0.8-1.6mol/L, the concentration of the second ammonium bicarbonate solution is 2.5-3.0mol/L, and the concentration of the third ammonium bicarbonate solution is 1.5-2.0mol/L;
(2) Adding the mixed metal solution and the second ammonium bicarbonate solution into the first ammonium bicarbonate solution in a concurrent flow manner for reaction, and controlling the reaction temperature to be 40-45 ℃ until the specific surface area is 0.3-0.6cm 2 Crystal transformation and aluminum-doped cobalt carbonate crystal seeds per gram;
(3) And (3) adding the mixed metal solution and the third ammonium bicarbonate solution into the solution containing the crystal-transformation aluminum-doped cobalt carbonate crystal seeds obtained in the step (2) in a parallel flow manner, mixing and reacting until the granularity of the crystal-transformation aluminum-doped cobalt carbonate crystal seeds grows to 16.0-19.0 mu m, carrying out solid-liquid separation, washing and drying the obtained solid, and obtaining the crystal-transformation aluminum-doped cobalt carbonate.
2. The method for preparing crystal transition aluminum-doped cobalt carbonate according to claim 1, characterized in that: in the step (1), the concentration of cobalt ions in the mixed metal solution is 1.5-2.5mol/L, and the molar ratio of aluminum element to cobalt element is 0.001-0.01.
3. The method for preparing crystal transition aluminum-doped cobalt carbonate according to claim 2, characterized in that: and (3) carrying out the reaction in a reaction kettle, wherein in the step (2), the first ammonium bicarbonate solution is added into the reaction kettle as a base solution and heated, the mixed metal solution and the second ammonium bicarbonate solution are added in a parallel flow manner through a liquid adding pipe under a stirring state for reaction, when the liquid level in the reaction kettle reaches a set value, concentration is started, and the specific surface area of the generated seed crystal is monitored until the specific surface area of the seed crystal reaches a target value.
4. The preparation method of the crystal-transition aluminum-doped cobalt carbonate as claimed in claim 3, characterized in that: in the step (2), the base solution accounts for 20-30% of the total volume of the reaction kettle, the flow rate of the mixed metal solution is 200-300L/h, the flow rate of the second ammonium bicarbonate solution is 100-150L/h, when the liquid level in the reaction kettle reaches 80-85% of the total volume of the reaction kettle, concentration is started, and the mixed metal solution and the second ammonium bicarbonate solution are continuously introduced to stabilize the liquid level in the kettle at 80-85% of the total volume.
5. The preparation method of the crystal-transition aluminum-doped cobalt carbonate as claimed in claim 3, characterized in that: and (3) controlling the pH value of the reaction in the step (2) to be 7.0-8.5.
6. The preparation method of the crystal-transition aluminum-doped cobalt carbonate as claimed in claim 3, characterized in that: in the step (3), the mixed metal solution and the third ammonium bicarbonate solution are added in parallel through a liquid adding pipe on the premise of starting concentration, the flow rate of the mixed metal solution is 100-200L/h, the pH value of the reaction is controlled to be 7.8-8.2 by continuously adding the third ammonium bicarbonate solution, the liquid level in the kettle is stabilized to be 80% -85% of the total volume, and the sizes of the liquid adding pipes used for the mixed metal solution, the second ammonium bicarbonate solution and the third ammonium bicarbonate solution are the same.
7. The preparation method of the crystal-transition aluminum-doped cobalt carbonate as claimed in claim 3, characterized in that: in the step (3), the reaction temperature is increased to 60-80 ℃ at a heating rate of 10-30 ℃/h.
8. The preparation method of the crystal-transition aluminum-doped cobalt carbonate as claimed in claim 3, characterized in that: the number of the liquid adding pipes of the mixed metal solution in the step (3) is more than that of the liquid adding pipes of the mixed metal solution in the step (2), and the number of the liquid adding pipes of the third ammonium bicarbonate solution in the step (3) is more than that of the liquid adding pipes of the second ammonium bicarbonate solution in the step (2).
9. The method for preparing crystal-transition aluminum-doped cobalt carbonate according to claim 8, characterized in that: in the step (2), the number of the liquid adding pipes of the mixed metal solution and the second ammonium bicarbonate solution is one.
10. Use of the crystal-transition aluminum-doped cobalt carbonate prepared by the preparation method of any one of claims 1 to 9 in preparation of a lithium cobaltate cathode material.
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