CN112279307B - High-magnification lithium cobaltate and preparation method and application thereof - Google Patents
High-magnification lithium cobaltate and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-multiplying power lithium cobalt oxide and a preparation method and application thereof. The precursor slurry spray-dried powder primary particles are nanocrystallized by utilizing a centrifugal spray-drying tower, the prepared powder is sintered into monocrystalline particles at high temperature, and the monocrystalline particles can improve the compaction density and capacity of the material; the particles prepared by the pressure spray drying tower have high compactness, the particles can be agglomerated into an aggregate after high-temperature sintering, and the rate and the cycle performance of the material can be improved by the aggregated particles. The material prepared by blending the particles prepared by the two drying modes has large capacity and excellent multiplying power and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to high-rate lithium cobalt oxide, and a preparation method and application thereof.
Background
Lithium cobaltate is the primary positive electrode material in current commercial lithium ion batteries. The high-magnification lithium cobaltate is mainly used for high-power electronic appliances such as electronic cigarettes, electronic models (model airplane, model car and the like), wireless electronic toys and the like; researches prove that doping and coating are one of the most effective methods in improving the performance, particularly the high-rate performance, of the positive electrode material of the lithium ion battery, so that the stability of ion lattices can be improved, and the cycle performance of the material can be greatly improved.
The use of lithium cobaltate as a high-rate battery material requires control of the particle size and crystal size of the product. If the particle size is too large, discharge efficiency becomes low under high-rate conditions, and if the particle size is too small, processability of the product is affected, resulting in deterioration of safety and cycle performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide high-rate lithium cobalt oxide and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the high-rate lithium cobaltate comprises the following steps:
s1, adding cobalt acetate, lithium carbonate and water into a ball mill for wet mixing to prepare mixed slurry; preferably, the ratio of the amounts of the substances of elemental lithium and elemental cobalt in the mixed slurry is 1.0-1.2:1.
s2, after the mixed slurry is subjected to primary drying by using a centrifugal spray drying tower, continuously heating and drying the mixed slurry, crushing the obtained dried material by using a ball mill, and collecting 150-300 mesh powder to obtain lithium carbonate-cobalt acetate precursor composite powder A1. Preferably, the air inlet temperature of the centrifugal spray drying tower is 200-350 ℃, and the air outlet temperature is 90-150 ℃; the temperature of heating and drying is 200-400 ℃.
S3, mixing the lithium carbonate-cobalt acetate precursor composite powder A1 with water, and performing wet ball milling to obtain ball milling slurry; after preliminary drying is carried out on ball-milling slurry by using a pressure spray drying tower, heating and drying are carried out on the ball-milling slurry continuously to obtain lithium carbonate-cobalt acetate precursor composite powder A2; preferably, the air inlet temperature of the pressure type spray drying tower is 260 ℃ and the air outlet temperature is 100-150 ℃; the temperature of heating and drying is 200-400 ℃.
S4, mixing the lithium carbonate-cobalt acetate precursor composite powder A1 prepared in the step S2 with the lithium carbonate-cobalt acetate precursor composite powder A2 prepared in the step S3 according to a mass ratio of 1-5:1, and calcining to obtain massive lithium cobaltate; and crushing the blocky lithium cobaltate by using an airflow crusher to obtain a final product. Preferably, the calcination temperature is 800-1000 ℃ and the time is 8-14h.
It is another object of the present invention to provide a high rate lithium cobaltate prepared by the above-described preparation method.
A third object of the present invention is to provide the use of the high-rate lithium cobaltate as described above as a positive electrode material in a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The principle of drying by using a centrifugal spray drying tower is as follows: the mixed slurry is thrown out of a rotary table under the action of centrifugal force in a high-speed rotary table of a centrifugal spray drying tower to be atomized, and then the mixed slurry is contacted with hot air to quickly evaporate water to obtain dry powder. The method can make the primary particles of the material nano, the powder prepared by centrifugal spray drying is sintered at high temperature to form monocrystalline particles, and the monocrystalline particles can improve the compaction density and capacity of the material; the principle of drying by using the pressure type spray drying tower is as follows: the high-pressure feed liquid is sent into a pressure atomizer to be atomized into small liquid drops, the atomized liquid drops (with greatly increased surface area) are fully contacted with hot air, the drying is rapidly completed, and the finished product of the agglomerate fine particles is formed in the drying process. The powder particles prepared by the method have high compactness, the powder is an aggregate after high-temperature sintering, and the aggregate particles can improve the multiplying power and the cycle performance of the material. The material prepared by blending the particles prepared by the two drying modes has large capacity and excellent multiplying power and cycle performance.
(2) The invention utilizes wet ball milling to uniformly mix the precursor slurry, so that the components are uniformly distributed.
(3) The lithium cobaltate prepared by the invention has uniform particle size distribution and excellent multiplying power performance and cycle performance by utilizing a spray technology.
Drawings
Fig. 1 is an SEM photograph of the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in step S2 of example 1.
Fig. 2 is an SEM photograph of the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in step S3 of example 1.
Fig. 3 is an SEM photograph of the lithium cobaltate powder obtained in example 1 at a magnification of 3000.
Fig. 4 is a graph showing the results of 80C rate performance test of lithium cobaltate button cell prepared from the lithium cobaltate prepared in example 1 and comparative example 1.
Detailed Description
The invention will be further illustrated with reference to examples. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, preparing mixed slurry: 200kg of cobalt acetate is taken and added into a ball mill, and the molar ratio of lithium to cobalt is 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
filling the precursor composite powder into a sagger with 320mm multiplied by 85mm, shaking uniformly after the sagger filling is finished, marking grids and scribing, sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃, and further removing the moisture of the lithium carbonate-cobalt acetate precursor composite powder;
and crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute, the ball milling time is 30 minutes, and the ball milling particle size of the powder passes through a 150-mesh screen to obtain the lithium carbonate-cobalt acetate precursor composite powder A1. The SEM photograph of the lithium carbonate-cobalt acetate precursor composite powder A1 is shown in fig. 1, and it can be seen from fig. 1 that the lithium carbonate-cobalt acetate precursor prepared by centrifugal spray drying is sintered and crushed into single crystal particles with small particle size and wide distribution. The particle with the morphology has obvious improvement on the tap density and the discharge capacity of the product.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain ball milling slurry. Drying ball-milling slurry by adopting a pressure spray drying tower, preparing precursor slurry powder with high compactness at an inlet air temperature of 260 ℃ and a discharge outlet temperature of 120 ℃, and continuously placing the material in a high-temperature calciner with a temperature of 300 ℃ for sintering for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness; SEM photographs of the lithium carbonate-cobalt acetate precursor composite powder A2 are shown in fig. 2, and it can be seen from fig. 2 that the precursor of A1 prepared by the pressure type spray drying tower is an agglomerate particle. The agglomerated particles not only can improve the multiplying power performance of the product, but also can make the cycle performance more excellent.
S4, filling the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with the mass ratio of A2:A1=2:1 of 320mm multiplied by 85mm, shaking uniformly after the sagger filling is finished, marking off, and sintering in a high-temperature calciner with the temperature of 850 ℃ for 10 hours to obtain the blocky lithium cobaltate.
And crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the airflow crusher is 5Hz, and the feeding frequency is 15Hz, so that the secondary particle spheroid high-magnification lithium cobaltate finished product with high agglomeration of small particles is finally obtained.
Example 2
S1, preparing mixed slurry: 200kg of cobalt acetate is taken and added into a ball mill, and the molar ratio of lithium to cobalt is 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
the precursor powder was placed in a 320mm×320mm×85mm sagger, 4 kg/sagger, and after the loading was completed, the sagger was shaken well and scribed. Sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃ to further remove the water of the lithium carbonate-cobalt acetate precursor composite powder;
crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute; ball milling is carried out for 30 minutes, the powder ball milling particle size is filtered by a 150-mesh screen, and the lithium carbonate-cobalt acetate precursor composite powder A1 is obtained.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain slurry. Drying ball-milling slurry by adopting a pressure type spray drying tower, wherein the inlet air temperature is 260 ℃, the outlet air temperature is 120 ℃, preparing precursor slurry powder with high compactness, and sintering the precursor powder in a high-temperature calciner with the temperature of 300 ℃ for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness;
s4, loading the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with the mass ratio of A2:A1=3:1 of 320mm multiplied by 85mm, shaking uniformly after the sagger loading is completed, and marking. And (3) burning in a high-temperature calciner with the temperature of 850 ℃ for 10 hours to obtain blocky lithium cobaltate.
Crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz; and the feeding frequency is 15Hz, and finally, the secondary particle spheroid high-multiplying-power lithium cobaltate finished product with high agglomeration of small particles is obtained.
Example 3
S1, preparing mixed slurry: 200kg of cobalt acetate is taken and added into a ball mill, and the molar ratio of lithium to cobalt is 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
the precursor composite powder is filled into a sagger with 320mm multiplied by 85mm, 4 kg/sagger, and after the sagger filling is completed, the sagger is shaken uniformly and is marked. Sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃ to further remove the water of the lithium carbonate-cobalt acetate precursor composite powder;
crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute; ball milling is carried out for 30 minutes, the powder ball milling particle size is filtered by a 150-mesh screen, and the lithium carbonate-cobalt acetate precursor composite powder A1 is obtained.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain slurry. Drying ball-milling slurry by adopting a pressure type spray drying tower, wherein the inlet air temperature is 260 ℃, the outlet air temperature is 120 ℃, preparing precursor slurry powder with high compactness, and sintering the precursor powder in a high-temperature calciner with the temperature of 300 ℃ for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness;
s4, filling the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with the mass ratio of A2:A1=4:1 of 320mm multiplied by 85mm, and shaking uniformly and marking after the sagger filling is completed, wherein the weight ratio is 5 kg/sagger. And (3) burning in a high-temperature calciner with the temperature of 850 ℃ for 10 hours to obtain blocky lithium cobaltate.
Crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz; and the feeding frequency is 15Hz, and finally, the secondary particle spheroid high-multiplying-power lithium cobaltate finished product with high agglomeration of small particles is obtained.
Example 4
S1, preparing mixed slurry: 200kg of cobalt acetate is taken and added into a ball mill, and the molar ratio of lithium to cobalt is 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
the precursor composite powder is filled into a sagger with 320mm multiplied by 85mm, 4 kg/sagger, and after the sagger filling is completed, the sagger is shaken uniformly and is marked. Sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃ to further remove the water of the lithium carbonate-cobalt acetate precursor composite powder;
crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute; ball milling is carried out for 30 minutes, the powder ball milling particle size is filtered by a 150-mesh screen, and the lithium carbonate-cobalt acetate precursor composite powder A1 is obtained.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain slurry. Drying ball-milling slurry by adopting a pressure type spray drying tower, wherein the inlet air temperature is 260 ℃, the outlet air temperature is 120 ℃, preparing precursor slurry powder with high compactness, and sintering the precursor powder in a high-temperature calciner with the temperature of 300 ℃ for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness;
s4, loading the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with the mass ratio of A2:A1=2:1 of 320mm multiplied by 85mm, shaking uniformly after the sagger loading is completed, and marking. The mixture was burned in a high temperature calciner at 900℃for 10 hours. To obtain blocky lithium cobalt oxide.
Crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz; and the feeding frequency is 15Hz, and finally, the secondary particle spheroid high-multiplying-power lithium cobaltate finished product with high agglomeration of small particles is obtained.
Example 5
S1, preparing mixed slurry: 200kg of cobalt acetate is taken and added into a ball mill, and the molar ratio of lithium to cobalt is 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
the precursor composite powder is filled into a sagger with 320mm multiplied by 85mm, 4 kg/sagger, and after the sagger filling is completed, the sagger is shaken uniformly and is marked. Sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃ to further remove the water of the lithium carbonate-cobalt acetate precursor composite powder;
crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute; ball milling is carried out for 30 minutes, the powder ball milling particle size is filtered by a 150-mesh screen, and the lithium carbonate-cobalt acetate precursor composite powder A1 is obtained.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain slurry. Drying ball-milling slurry by adopting a pressure spray drying tower, preparing precursor slurry powder with high compactness at an inlet air temperature of 260 ℃ and a discharge outlet temperature of 120 ℃, and sintering the precursor powder in a high-temperature calciner with a temperature of 300 ℃ for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness;
s4, filling the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with 320mm multiplied by 85mm according to the proportion of A2:A1= (2:1), and shaking uniformly and marking out after the sagger filling is completed, wherein the sagger is 5 kg/sagger. The mixture was burned in a high temperature calciner at 850℃for 12 hours. To obtain blocky lithium cobalt oxide.
Crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the airflow crusher is 5Hz; and the feeding frequency is 15Hz, and finally, the secondary particle spheroid high-multiplying-power lithium cobaltate finished product with high agglomeration of small particles is obtained.
Example 6
S1, adding 200kg of cobalt acetate into a ball mill, and then adding the cobalt acetate into the ball mill according to a lithium cobalt molar ratio of 1.02:1 adding lithium carbonate, and then adding deionized water into a ball milling tank, wherein the deionized water accounts for 2/3 of the volume of the tank. Mixing for 25 minutes at 500 rpm in a high-speed ball mill, and uniformly mixing to obtain mixed slurry;
s2, centrifugal spray drying crystallization: adding a three-stage filtering and purifying system into an air inlet system of a spray drying tower, controlling the air inlet temperature to be 250 ℃ and the air outlet temperature to be 120 ℃ after the air inlet reaches the efficiency of a sub-efficient filter H11, enabling the rotational speed of an atomizer to be 15000r/min and the feeding rate to be 3kg/min, drying the materials through the centrifugal spray drying tower, and adding a linear vibrating screen with a water cooling system at a discharge port, wherein the material outlet temperature is less than or equal to 60 ℃, so as to obtain lithium carbonate-cobalt acetate precursor composite powder;
the precursor powder was placed in a 320mm×320mm×85mm sagger, 4 kg/sagger, and after the loading was completed, the sagger was shaken well and scribed. Sintering for 3 hours in a high-temperature calciner with the temperature of 300 ℃ to further remove the water of the lithium carbonate-cobalt acetate precursor composite powder;
crushing the dried material by using a ball mill, wherein the rotating speed of the ball mill is 500 revolutions per minute; ball milling is carried out for 30 minutes, the powder ball milling particle size is filtered by a 150-mesh screen, and the lithium carbonate-cobalt acetate precursor composite powder A1 is obtained.
And S3, adding deionized water into the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 for wet ball milling for 4 hours to obtain slurry. Drying ball-milling slurry by adopting a pressure type spray drying tower, wherein the inlet air temperature is 260 ℃, the outlet air temperature is 120 ℃, preparing precursor slurry powder with high compactness, and sintering the precursor powder in a high-temperature calciner with the temperature of 300 ℃ for 7 hours to obtain lithium carbonate-cobalt acetate precursor composite powder A2 with high compactness;
s4, filling the lithium carbonate-cobalt acetate precursor composite powder A1 obtained in the step S2 and the lithium carbonate-cobalt acetate precursor composite powder A2 obtained in the step S3 into a sagger with 320mm multiplied by 85mm according to the proportion of A2:A1= (2:1), and shaking uniformly and marking out after the sagger filling is completed, wherein the sagger is 5 kg/sagger. The mixture was burned in a high temperature calciner at 800℃for 10 hours. To obtain blocky lithium cobalt oxide.
Crushing the blocky lithium cobaltate by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz; and the feeding frequency is 15Hz, and finally, the secondary particle spheroid high-multiplying-power lithium cobaltate finished product with high agglomeration of small particles is obtained.
Comparative example
(1) Primary mixing: taking 100Kg of cobalt acetate, adding lithium carbonate into a high-speed mixer according to the molar ratio of lithium to cobalt (1.02:1), mixing for 25 minutes at 500 revolutions per minute in the high-speed mixer, and discharging after uniform mixing;
(2) And (5) loading the pot at one time: filling the mixture obtained in the step 1) into a sagger with the thickness of 320mm multiplied by 85mm, and shaking up and lattice marking after the completion of filling of 4 kg/sagger;
(3) Primary sintering: sintering the bowl-filling scribing material obtained in the step 2) for 10 hours in a high-temperature calciner with the temperature of 900 ℃;
(4) Primary crushing: crushing the primary sintering material obtained in the step 3) by using an airflow crusher, wherein the classification frequency of the crusher is 5Hz; the feeding frequency is 20Hz, and the primary sintering crushed lithium cobalt oxide is obtained.
(5) And (5) secondary bowl loading: filling the secondary batching mixture obtained in the step 5) into a sagger with the thickness of 320mm multiplied by 85mm, and shaking up and lattice marking after the sagger filling is completed, wherein the weight of the secondary batching mixture is 5 kg/sagger;
(6) Secondary sintering: sintering the secondary bowl-filling scribing material obtained in the step 6) for 10 hours in a high-temperature calciner with the temperature of 900 ℃;
(7) Secondary crushing: crushing the secondary sintering high-rate lithium cobaltate obtained in the step 7) through an airflow crusher, wherein the classification frequency of the crusher is 5Hz; and the feeding frequency is 20Hz, and finally the lithium cobaltate finished product is obtained.
Physical and chemical test results show that the median particle size of the lithium cobaltate prepared in example 1 is 5.53 μm and the tap density is 2.70g/cm 3 Specific surface area of 0.686m 2 /g。
The lithium cobaltate sample prepared in example 1 was used as a positive electrode active material, graphite was used as a negative electrode, and a soft pack battery was assembled and the battery was subjected to an electrical property test using a battery property tester. The charge-discharge cut-off voltage is 3-4.2V, the charge multiplying power is 0.2C, the measured specific capacity of the first 1C discharge is 157.7mAh/g, and the discharge capacities under different discharge multiplying powers of 20C, 30C, 60C and 80C respectively reach 97.9%, 97.1%, 94.3% and 92.6% of the discharge capacity of 1C.
The median particle size of the lithium cobaltate prepared in comparative example was 6.22. Mu.m, and tap density was 2.51g/cm 3 A specific surface area of 0.571m 2 /g。
The lithium cobaltate sample prepared in the comparative example is used as an active material of a positive electrode, graphite is used as a negative electrode to be assembled into a soft-packed battery, and the battery performance tester is used for testing the electrical performance of the battery. The charge-discharge cut-off voltage is 3-4.2V, the charge multiplying power is 0.2C, the measured specific capacity of the first 1C discharge is 149.8mAh/g, and the discharge capacities under different discharge multiplying powers of 20C, 30C, 60C and 80C respectively reach 97.2%, 95.1%, 86.8% and 66.1% of the discharge capacity of 1C.
FIG. 3 is an SEM photograph of a lithium cobalt oxide powder obtained in example 1 of the present invention at a magnification of 3000. It can be seen that the lithium cobaltate prepared in example 1 is a spheroid particle formed by close fusion of small particles and high agglomeration and has uniform particle distribution. The lithium cobaltate with the morphology is more beneficial to maintaining structural stability when the material is discharged, and is particularly beneficial to being discharged at an ultra-high rate (80C).
Fig. 4 is a graph showing the results of the rate performance test of the lithium cobaltate soft pack 80C obtained in example 1 and comparative example 1, and it can be seen that the rate discharge performance of the lithium cobaltate soft pack 80C prepared in example 1 is significantly better than that of the comparative example.
TABLE 1 physical Properties of lithium cobalt oxide obtained in examples 1 and 2 of the present invention and comparative example
Table 2 results of the electrical property test of inventive examples 1, 2 and comparative example lithium cobaltate
From Table 1, it is understood that the lithium cobaltate prepared in the examples has a smaller particle size than the comparative examples, and the tap density and the ratio are larger than those of the comparative examples. The high tap density can effectively improve the energy density of the battery, and the larger ratio meter can enable the material to be fully contacted with the electrolyte, so that the rate performance is improved. The test results in Table 2 also show that the lithium cobaltate prepared in the examples has significantly better high rate performance than the comparative examples, especially at discharge above 60C.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A preparation method of high-rate lithium cobaltate is characterized in that: the method comprises the following steps:
s1, adding cobalt acetate, lithium carbonate and water into a ball mill for wet mixing to prepare mixed slurry;
s2, carrying out primary drying on the mixed slurry by using a centrifugal spray drying tower, continuously heating and drying the mixed slurry, and crushing and screening the obtained dried material to obtain lithium carbonate-cobalt acetate precursor composite powder A1; the air inlet temperature of the centrifugal spray drying tower is 200-350 ℃, and the air outlet temperature is 90-150 ℃; the temperature of heating and drying is 200-400 ℃; sintering and crushing the lithium carbonate-cobalt acetate precursor prepared by centrifugal spray drying to obtain monocrystal particles with small granularity and wide distribution;
s3, mixing the lithium carbonate-cobalt acetate precursor composite powder A1 with water, and performing wet ball milling to obtain ball milling slurry; after preliminary drying is carried out on ball-milling slurry by using a pressure spray drying tower, heating and drying are carried out on the ball-milling slurry continuously to obtain lithium carbonate-cobalt acetate precursor composite powder A2; the inlet air temperature of the pressure spray drying tower is 260 ℃ and the outlet air temperature is 100-150 ℃; the temperature of heating and drying is 200-400 ℃; the precursor prepared by the lithium carbonate-cobalt acetate precursor composite powder A1 through a pressure spray drying tower is agglomerate grains;
s4, mixing the lithium carbonate-cobalt acetate precursor composite powder A1 prepared in the step S2 with the lithium carbonate-cobalt acetate precursor composite powder A2 prepared in the step S3, and calcining to obtain blocky lithium cobaltate; crushing the blocky lithium cobaltate to obtain a final product; the calcination temperature is 800-1000 ℃ and the calcination time is 8-14h.
2. The method of manufacturing according to claim 1, characterized in that: in the step S1, the ratio of the amounts of substances of the element lithium and the element cobalt in the mixed slurry is 1.0-1.2:1.
3. the method of manufacturing according to claim 1, characterized in that: in the step S2, the dried material is crushed by a ball mill, and 150-300 mesh powder is collected after crushing.
4. The method of manufacturing according to claim 1, characterized in that: in the step S4, the mixing mass ratio of the lithium carbonate-cobalt acetate precursor composite powder A1 to the lithium carbonate-cobalt acetate precursor composite powder A2 is 1-5:1.
5. The method of manufacturing according to claim 1, characterized in that: in step S4, the bulk lithium cobalt oxide is pulverized by a jet mill.
6. A high rate lithium cobaltate produced by the production process according to any one of claims 1 to 5.
7. The use of the high-rate lithium cobaltate as defined in claim 6 as a positive electrode material in a lithium ion battery.
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