CN108439489B - Preparation method of high-tap-density battery-grade cobaltosic oxide - Google Patents
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Abstract
The invention discloses a preparation method of high-tap battery grade cobaltosic oxide. The method comprises the following steps: adding the precipitant solution and the seed crystal into a reaction vessel simultaneously; adding the cobalt solution into a reaction container by a reverse feeding method to prepare a cobalt salt precursor; then washing and dehydrating to ensure that the water content of the filter cake is less than 25 percent; and (3) feeding the mixture into a calcining furnace for calcining, then carrying out grading sieving to obtain the high-tap-density and sphere-like battery grade cobaltosic oxide, further removing magnetic metal foreign matters by magnetism, and controlling the content of the magnetic metal foreign matters to be below 1ppm so as to obtain the high-quality battery grade cobaltosic oxide. The obtained sphere-like battery grade cobaltosic oxide has the characteristics of high tap density, high chemical purity, wide raw material adaptability range, easy control of crystal grain size, uniform granularity composition, good consistency, low content of magnetic substances, simple process, easy operation, low cost, stable product quality, energy conservation and environmental protection, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of battery materials, in particular to a preparation method of high-tap-density battery-grade cobaltosic oxide.
Background
Tricobalt tetraoxide having a spinel structure in which Co (II) ion tetrahedra are surrounded by oxygen atoms and Co (III) ion octahedra are surrounded by oxygen atoms. The cobaltosic oxide is an important inorganic functional powder material, and the size and the shape of the particle of the cobaltosic oxide have obvious influence on the physical and chemical properties of the cobaltosic oxide. However, most of the cobaltosic oxide prepared by the manufacturers at present has wide particle size distribution, low density, high impurity content and low quality. Lithium ion batteries are favored because of their advantages of high voltage, high energy density, long cycle life, little environmental pollution, and the like. In recent years, with the further increase of the demand of small-sized mobile power supplies and power supplies of power automobiles, good opportunities are created for the development of the lithium ion battery industry. The rapid development of the lithium ion battery industry has driven the positive electrode materials to be: the development of cobalt-based positive electrode materials such as lithium cobaltate, lithium nickel cobalt manganate and the like has led to a great increase in demand for cobalt-based positive electrode materials for lithium ion batteries. The cobaltosic oxide is a raw material of lithium cobaltate which is a positive electrode material of the lithium ion battery. Due to the special requirements of the chemical components and physical properties of cobalt-based cathode materials, the chemical components and physical properties of the raw material cobaltosic oxide have a great influence on the electrochemical properties of cathode materials such as lithium cobaltate. Generally, the cobaltosic oxide is required to be spherical or spheroidal and has uniform particle size distribution.
Traditionally, precipitation-thermal decomposition process routes have been used to prepare battery grade cobaltosic oxide. The method comprises the steps of precipitating soluble cobalt salt to generate insoluble cobalt salt, and then thermally decomposing to prepare cobaltosic oxide. The cobaltosic oxide produced by the traditional method is amorphous, the particle size range of powder particles is wider and uneven, and the tap density of the generated anode material is low, so that the battery volume is large, and the requirement of the development of the current lithium ion battery industry cannot be met; meanwhile, the traditional method has higher requirements on morphology control and impurity control, and the adaptability of the original auxiliary material is narrower.
Because the particle size distribution, density and microscopic morphology of the cobaltosic oxide product and the particle size and particle crystallinity of the precursor of the cobaltosic oxide product have great influence, the control on various operating conditions in the process of preparing the precursor cobalt salt is also important, part of process methods are complex, the content of magnetic metal foreign matters can not be effectively controlled, and the defects of poor battery consistency, poor electrochemical performance, poor safety performance and the like are caused.
Disclosure of Invention
The invention aims to provide a method for manufacturing sphere-like battery grade cobaltosic oxide, which has the advantages of high tap density, high chemical purity, wide raw material adaptability range, easily controllable grain size, uniform grain size composition, good consistency and low magnetic content.
In order to achieve the aim, the invention provides a preparation method of high-tap battery grade cobaltosic oxide, which is characterized by comprising the following steps of:
preparing a cobalt salt precursor: adding the precipitant solution and the seed crystal into a reaction vessel simultaneously; adding the cobalt solution into a reaction vessel by a reverse feeding method, preferably, the molar ratio of cobalt in the cobalt solution to precipitator in the precipitator solution is 1.0 to (2.5-4.0); controlling the reaction temperature to be 30-60 ℃, the stirring speed to be 30-500 rpm, and the precipitation time to be 300-600 min, and preparing a precipitate of the cobalt salt, namely a cobalt salt precursor;
and (3) dehydrating: washing the cobalt salt precursor with deionized water at 30-80 ℃ and then dehydrating to ensure that the water content of a filter cake is less than 25% so as to facilitate the tap, BET and morphology indexes of subsequent calcination;
and (3) calcining: feeding the dehydrated cobalt salt precursor into a calcining furnace, and calcining by adopting a continuous feeding and synchronous dehydration calcining mode;
grading and sieving: and (3) grading and sieving the calcined product to obtain high-tap-density and sphere-like battery grade cobaltosic oxide, wherein the granularity of the battery grade cobaltosic oxide is that D10 is more than or equal to 4 mu m, D50: 10.0-18.0 μm, D97 is less than or equal to 40 μm, consistency: 0.2 to 0.6;
demagnetizing: and (3) removing magnetic metal foreign matters from the battery-grade cobaltosic oxide obtained in the step through demagnetization, and controlling the content of the magnetic metal foreign matters to be less than 1ppm so as to obtain the high-quality battery-grade cobaltosic oxide.
Further, in the preparation step of the cobalt salt precursor, the precipitant solution is 100 g/L-260 g/L of precipitant aqueous solution;
optionally, the cobalt solution is 60 g/L-130 g/L of cobalt raw material aqueous solution.
Further, the precipitant is ammonium bicarbonate, ammonium carbonate, sodium carbonate or sodium bicarbonate;
optionally, the cobalt raw material is industrial cobalt salt, or a purified solution obtained after extraction of cobalt ore, cobalt waste and a cobalt intermediate product, or cobalt salt obtained by direct acidolysis of metal cobalt; preferably, the cobalt salt is cobalt chloride, cobalt sulfate or cobalt nitrate.
Further, in the step of preparing the cobalt salt precursor, the ratio of cobalt in the cobalt solution: the molar ratio of the precipitant in the precipitant solution is 1.0 to (1.7-4.0).
Further, in the preparation step of the cobalt salt precursor, the seed crystal is cobaltosic oxide or cobalt carbonate; preferably, the weight of the seed crystal is 20-50% of the weight of the target product, the D50 of the seed crystal is 5-10 μm, and the consistency is 0.1-0.7.
Further, in the dehydration step, deionized water with the volume 1-3 times of the volume of the material is used for washing the cobalt salt precursor, and the water temperature is controlled at 20-80 ℃.
Further, in the calcining step, the calcining furnace is a box furnace or a continuous rotary kiln.
Further, in the calcining step, the dehydrated cobalt salt precursor is calcined at 450-1000 ℃, and the calcination is kept for 2-5 hours.
Further, dry demagnetization or wet demagnetization is adopted in the demagnetization step.
The method comprises the steps of taking cobalt salts such as cobalt chloride, cobalt sulfate and cobalt nitrate as cobalt raw materials, dissolving cobalt and purifying to obtain cobalt liquid (or a purified solution obtained after extraction of cobalt ore, cobalt waste and cobalt intermediate products, or a cobalt salt obtained by direct acidolysis of metal cobalt), preparing a precursor by adopting a crystal seed control crystallization precipitation method, adding the prepared precipitator solution and cobaltosic oxide or cobalt carbonate crystal seed into a reaction container together, adding the cobalt solution with a certain concentration into the reaction container by adopting a reverse feeding method according to a certain molar ratio, and effectively controlling chemical impurities, crystal crystallinity, granularity and the like of the precursor by controlling parameters such as reaction temperature, feeding speed, precipitation time, stirring speed and the like to synthesize a precipitate precursor; and (3) directly putting the water-containing filter cake into calcination after washing and dehydration, controlling the grain size and the crystal morphology by synchronous dehydration calcination, then carrying out grading sieving, and finally removing magnetic metal foreign matters to finally obtain the high-quality and high-tap battery grade cobaltosic oxide.
The high-quality high-tap battery grade cobaltosic oxide prepared by the method is characterized in that: the chemical purity is high, and each index of elements meets the requirement of battery-grade standard; apparent Density (AD)1.0g/cm3～2.0g/cm3(ii) a Tap Density (TD)2.0g/cm3～3.5g/cm3The particle size is normally distributed, D10 is more than or equal to 4 mu m, D50: 10.0-18.0 μm, D97 is less than or equal to 40 μm, consistency: 0.2 to 0.6; the content of metallic foreign matters (such as Fe, Ni, Cr, Zn and the like) is less than or equal to 1ppm, and the index requirements of lithium cobaltate raw materials used by high-end lithium ion batteries are completely met.
The preparation method of the high-tap battery grade cobaltosic oxide improves the traditional precipitation-thermal decomposition process route, optimizes the preparation process of the cobalt salt precursor, has wider adaptability, and better controls various operation conditions in the process of preparing the precursor cobalt salt. The method comprises the steps of firstly, controlling crystallization precipitation by adopting crystal seeds to control the crystallinity of a precursor, effectively controlling the crystallinity of the precursor, simultaneously adding the crystal seeds to obtain the required morphology, and transforming cobalt carbonate or cobaltosic oxide with different morphologies and granularities by the crystal seed precipitation to produce products with the same morphology; secondly, the method directly feeds and calcines the water-containing precursor, and can better control the feeding process through continuous feeding and synchronous dehydration and calcination; thirdly, the calcined product is graded and sieved, and the granularity, the loose loading, the tap density and other physical indexes of the final product are controlled; finally, the invention removes the magnetic metal foreign matters by dry demagnetization or wet demagnetization, controls the content of the magnetic metal foreign matters (such as Fe, Ni, Cr, Zn and the like) to be less than or equal to 1ppm, has more method selectivity and greatly improves the safety of the lithium ion battery.
The invention has the advantages that:
1. the manufacturing method of the battery-grade cobaltosic oxide has the advantages of simple process, easy operation, low cost, stable product quality, energy conservation and environmental protection, and is suitable for industrial production.
2. The microcosmic appearance of the cobaltosic oxide product prepared by the invention is similar to spherical, the powder has good fluidity and uniform granularity, the cobaltosic oxide product is in normal distribution with narrower wave peak, D10 is more than or equal to 4 mu m, D50: 10.0-18.0 μm, D97 is less than or equal to 40 μm, consistency: 0.2 to 0.6; tap density of 2.0g/cm3～3.5g/cm3。
3. The precipitant solution and the crystal seed are added into the reaction vessel at the same time, the cobalt solution is added into the reaction vessel by a back feeding method, the crystal seed control crystallization precipitation method is adopted to produce the precursor, the appearance and the granularity of the precursor can be further controlled, the crystallinity of the precursor is improved, and products with the same appearance can be produced by different crystal seeds.
4. The water-containing precursor is directly fed and calcined, and the feeding process can be better controlled through continuous feeding and synchronous dehydration and calcination.
5. Removing the metal magnetic foreign matters by dry demagnetization or wet demagnetization, and controlling the content of the metal magnetic foreign matters (such as Fe, Ni, Cr, Zn and the like) to be below 1ppm to obtain the high-quality battery-grade cobaltosic oxide.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of high tap cobaltosic oxide of example 1.
Figure 2 laser particle size plot of high tap cobaltosic oxide of example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) image of high tap cobaltosic oxide of example 2.
Fig. 4 is a laser particle size plot of the high tap cobaltosic oxide of example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
preparing industrial-grade cobalt sulfate into a solution with the cobalt concentration of 75 g/L by using deionized water, preparing ammonium bicarbonate into a precipitator solution with the concentration of 260 g/L by using the deionized water in a reaction container, simultaneously adding 40% of cobaltosic oxide with the weight of a target product as a seed crystal (the seed crystal D50:8.5 mu m, consistency: 0.32), determining the using amount of the cobalt solution according to the molar ratio of the cobalt solution to the precipitator solution, adding the cobalt solution into the reaction container by using a back feeding method, controlling the reaction temperature to be 55 ℃, the stirring speed to be 200rpm, precipitating for 300min by using the seed crystal to control the crystallization precipitation method, preparing a precursor by using 30 ℃ deionized water and water with the volume of 1 time of the materialWashing, dewatering, directly feeding a filter cake with the water content of 22%, calcining at 550-800 ℃ in a continuous rotary kiln, controlling the retention time of the material in the kiln to be 2 hours, directly and continuously cooling after discharging from the tail of the kiln, and sieving and grading; removing the metal magnetic foreign matters through wet demagnetization to obtain spherical cobaltosic oxide powder, D10: 8.06 μm, D50: 14.06 μm, D90: 22.68 μm, consistency: 0.34, TD: 2.08g/cm3. (the SEM image and the laser particle size are shown in FIG. 1 and FIG. 2). As can be seen from FIGS. 1 and 2, the obtained cobaltosic oxide has a spheroidal micro-morphology, good powder flowability, uniform particle size and normal distribution with narrow peaks.
Example 2:
preparing industrial grade cobalt nitrate into a solution with cobalt concentration of 100 g/L by using deionized water, preparing ammonium carbonate into a precipitator solution with concentration of 200 g/L by using the deionized water in a reaction container, simultaneously adding 37% of cobalt carbonate with target product weight as a seed crystal (seed crystal D50:10.68 mu m, consistency: 0.30), determining the using amount of the cobalt solution according to the mole ratio of the cobalt to the precipitator, adding the cobalt solution into the reaction container by using a reverse feeding method, controlling the reaction temperature to be 45 ℃, the stirring speed to be 250rpm, the precipitation time to be 240min, preparing a precursor by using a crystal precipitation control method, washing the precursor by using the deionized water with the temperature of 25 ℃ and the water amount of 1.5 times of the volume of the material, dehydrating a filter cake to be 27%, directly feeding the filter cake into a continuous rotary kiln, calcining at the temperature of 550-800 ℃, controlling the residence time of the material in the kiln to be 2 hours, directly cooling and grading the material after discharging the tail of the kiln, removing magnetic foreign matters by using a magnetic oxidation method to obtain quasi-spherical cobalt nitrate powder with the weight of 100 g/368, 54.7: 54.7, 27.7: 7, 27.7: 7.7, 27.14 mu m, 27, TD 21/3614.14 m, 20.0.0.0.3. (the SEM image and the laser particle size are shown in FIGS. 3 and 4). As can be seen from FIGS. 3 and 4, the obtained cobaltosic oxide has a spheroidal micro-morphology, good powder flowability, uniform particle size and normal distribution with narrow peaks.
Example 3:
preparing industrial-grade cobalt chloride into a solution with the cobalt concentration of 130 g/L by using deionized water,preparing sodium bicarbonate into precipitator solution with concentration of 260 g/L by using deionized water in a reaction container, simultaneously adding 50% of cobaltosic oxide with target product weight as seed crystal (seed crystal D50:8.01 mu m, consistency: 0.34), determining the dosage of the cobalt solution by using the cobalt solution and the precipitator solution according to the mol ratio of 1.0: 1.96, adding the cobalt solution into the reaction container by a back feeding method, controlling the reaction temperature to be 50 ℃, the stirring speed to be 250rpm, the precipitation time to be 300min, preparing a precursor by using a seed crystal controlled crystallization precipitation method, washing the precursor by using 30 ℃ deionized water with 1 time of the volume of the material, dehydrating, directly feeding the obtained product into a continuous rotary kiln to calcine at 550-800 ℃, controlling the retention time of the material in the kiln to be 3 hours, directly and continuously cooling and sieving after discharging the kiln tail, removing magnetic metal foreign matters by a wet method to obtain spherical-like cobaltosic oxide powder, D10: 8.16 mu m, D50: 14.16 mu m, TD 90.32 mu m, TD: 10.32 g/78 g, and consistency: 2.32 cm3. The microcosmic appearance of the obtained cobaltosic oxide is similar to a sphere, the powder has good fluidity and uniform granularity, and the particle is in normal distribution with narrower wave crest.
Example 4:
preparing industrial cobalt chloride into a solution with a cobalt concentration of 60 g/L by using deionized water, preparing sodium carbonate into a precipitator solution with a concentration of 200 g/L by using the deionized water in a reaction container, adding 35% of cobalt carbonate with the target product weight as a seed crystal (the seed crystal D50:11.68 mu m, the consistency: 0.31, determining the use amount of the cobalt solution according to the mole ratio of the cobalt solution to the precipitator 1.0: 1.76, adding the cobalt solution into the reaction container by a reverse feeding method, controlling the reaction temperature to be 45 ℃, the stirring speed to be 200rpm, precipitating for 270min, preparing a precursor by a crystal precipitation method under the control of the seed crystal, washing the precursor by using deionized water with the temperature of 25 ℃ and water with the volume of 3 times of the volume of the material, dehydrating a filter cake with the water content of 30%, directly feeding the precursor into a continuous rotary kiln, calcining at the temperature of 550-800 ℃, controlling the retention time of the material in the kiln to be 2.5 hours, directly cooling and grading the material after discharging from the tail of the kiln, and removing magnetic oxide metal foreign matters by a dry method, so as to obtain quasi-spherical cobalt chloride powder with the concentration of 368, 36.8.42 μm, D90: 22.12 μm, consistency: 0.28, TD: 2.55g/cm3. The microcosmic appearance of the obtained cobaltosic oxide is similar to a sphere, the powder has good fluidity and uniform granularity, and the particle is in normal distribution with narrower wave crest.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (9)
1. A preparation method of high tap density battery grade cobaltosic oxide is characterized by comprising the following steps:
preparing a cobalt salt precursor: adding a precipitant solution and seed crystals into a reaction container simultaneously, wherein the precipitant is ammonium bicarbonate, ammonium carbonate, sodium carbonate or sodium bicarbonate; adding the cobalt solution into a reaction vessel by a reverse feeding method, wherein the molar ratio of cobalt in the cobalt solution to precipitator in the precipitator solution is 1.0 to (2.5-4.0); controlling the reaction temperature to be 30-60 ℃, the stirring speed to be 30-500 rpm, and the precipitation time to be 300-600 min, and preparing a precipitate of the cobalt salt, namely a cobalt salt precursor; the seed crystal is cobaltosic oxide; the weight of the seed crystal is 20-50% of the weight of the target product, the D50 of the seed crystal is 5-10 mu m, and the consistency is 0.1-0.7;
and (3) dehydrating: washing the cobalt salt precursor with deionized water at 30-80 ℃ and then dehydrating to ensure that the water content of the filter cake is less than 25%;
and (3) calcining: feeding the dehydrated cobalt salt precursor into a calcining furnace, and calcining by adopting a continuous feeding and synchronous dehydration calcining mode;
grading and sieving: and (3) grading and sieving the calcined product to obtain high-tap-density and sphere-like battery grade cobaltosic oxide, wherein the granularity of the battery grade cobaltosic oxide is that D10 is more than or equal to 4 mu m, D50: 10.0-18.0 μm, D97 is less than or equal to 40 μm, consistency: 0.2 to 0.6;
demagnetizing: and (3) removing magnetic metal foreign matters from the battery-grade cobaltosic oxide obtained in the step through demagnetization, and controlling the content of the magnetic metal foreign matters to be less than 1ppm so as to obtain the high-quality battery-grade cobaltosic oxide.
2. The method for preparing cobaltosic oxide for high tap cell grade according to claim 1, wherein in the step of preparing the cobalt salt precursor, the solution of the precipitant is 100 g/L-260 g/L of the aqueous solution of the precipitant.
3. The method of claim 1, wherein the cobalt solution is an aqueous solution of 60 g/L-130 g/L of cobalt starting material.
4. The method for preparing cobaltosic oxide for high tap density batteries according to claim 3, wherein the cobalt material is industrial cobalt salt, or a purified solution obtained after extraction of cobalt ore, cobalt waste and cobalt intermediate, or cobalt salt obtained by direct acidolysis of metallic cobalt.
5. The method of claim 4, wherein the cobalt salt is cobalt chloride, cobalt sulfate, or cobalt nitrate.
6. The method for preparing cobaltosic oxide for high tap battery grade according to claim 1, wherein in the dehydration step, deionized water with the volume of 1-3 times of the material volume is used for washing the cobalt salt precursor.
7. The method of claim 1, wherein in the calcining step, the calciner is a box-type kiln or a continuous rotary kiln.
8. The method for preparing cobaltosic oxide for high tap battery grade according to claim 1, wherein in the calcining step, the dehydrated cobalt salt precursor is calcined at 450-1000 ℃ and stays for 2-5 h.
9. The method for preparing cobaltosic oxide for high tap battery grade according to claim 1, wherein the step of demagnetizing is performed by dry method or wet method.
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| CN108751264B (en) * | 2018-08-29 | 2020-02-07 | 常州市卓群纳米新材料有限公司 | Preparation method of large-particle cobaltosic oxide with D50 particle size of 30-40 mu m |
| CN109678215B (en) * | 2019-03-08 | 2020-12-01 | 张甘泉 | Preparation method of cobaltosic oxide with small and uniform particle size |
| CN112850802A (en) * | 2019-11-28 | 2021-05-28 | 荆门市格林美新材料有限公司 | Production process and production device of wide-distribution cobaltosic oxide |
| CN111874957A (en) * | 2020-06-30 | 2020-11-03 | 荆门市格林美新材料有限公司 | Production process of cobaltosic oxide precursor for superfine cobalt powder |
| CN112320855B (en) * | 2020-11-11 | 2023-02-14 | 金川集团股份有限公司 | Preparation method of medium-granularity cobaltosic oxide |
| CN113233515B (en) * | 2021-05-14 | 2023-03-10 | 衢州华友钴新材料有限公司 | Preparation method and calcining equipment of cobaltosic oxide particles |
| CN113716618B (en) * | 2021-09-01 | 2023-08-01 | 荆门市格林美新材料有限公司 | Preparation method of cobaltosic oxide with octahedral morphology |
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