CN108365183B - Ternary material with surface coated with aluminum oxide and preparation method thereof - Google Patents
Ternary material with surface coated with aluminum oxide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ternary material with an aluminum oxide coated surface and a preparation method thereof, wherein the preparation method comprises the following steps: mixing alkaline ternary precursor slurry and an aluminum salt solution for reaction, then carrying out aging and solid-liquid separation to obtain a ternary precursor with the surface coated with aluminum hydroxide, then mixing the ternary precursor with the surface coated with the aluminum hydroxide with a lithium source, sintering the mixed material, and obtaining the ternary material with the surface coated with the aluminum oxide after sintering. The preparation method has the advantages of simple process, low energy consumption, low equipment investment cost, high production efficiency and good coating effect, and the prepared ternary material is uniformly coated with the compact alumina layer on the surface and has high structural stability and high reliability of charge and discharge performance.
Description
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a ternary material with the surface coated with aluminum oxide and a preparation method thereof.
Background
The lithium ion battery anode material is widely used for power supply equipment such as power batteries, tool batteries, polymer batteries, cylindrical batteries, aluminum shell batteries and the like. Compared with other lithium ion battery anode materials such as lithium manganate and lithium iron phosphate, the lithium nickel cobalt manganese oxide material is very close to lithium cobaltate in electrochemical performance and processing performance, so that the lithium nickel cobalt manganese oxide material becomes a new battery material to gradually replace the lithium cobaltate, and becomes a favorite of a new generation of lithium battery ternary material.
The aluminum oxide is coated on the surfaces of the nickel cobalt lithium manganate and other ternary materials, so that the structural stability of the materials can be improved. At present, the existing method for coating the surface of a ternary material with alumina is to coat a ternary material finished product, which is mainly divided into two types, wherein one type is to add a sintered and crystallized ternary material into a liquid phase coating agent to emulsify and disperse coated particles and the ternary material, and then obtain the ternary material with the surface coated with alumina after drying and secondary sintering; and the other method is to coat an alumina layer on the surface of the sintered and crystallized ternary material by a liquid phase surface deposition technology, then carry out solid-liquid separation, and then carry out secondary sintering on the solid phase material to obtain the ternary material with the surface coated with alumina.
However, both of the above-mentioned prior art coating methods have the following drawbacks:
1) the process flow is long, the equipment investment is high, the energy consumption is high, the efficiency is low, a large amount of heat energy is consumed for drying and secondary sintering, and the cost is high;
2) if a more uniform precipitation coating effect is to be achieved, longer coating time is required, the condition control on the process is more difficult, and the stability of the product batch is poor;
3) alcohol dispersants or water are generally selected as coating dispersants, but the alcohol dispersants are high in cost and low in recovery rate, so that the cost is high, the ternary material is sensitive to water, particularly the high-nickel material, partial cations can be hydrolyzed and damaged in water, crystal grains on the surfaces of material particles lose inherent layered structures, the electrical property is reduced, the damage is irreversible, and the material particles are difficult to recover through later-stage secondary sintering.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a ternary material with the surface coated with alumina, which has the advantages of simple process, low energy consumption, low equipment investment cost, high production efficiency and good coating effect.
The technical scheme adopted by the invention is as follows:
a preparation method of a ternary material with the surface coated with alumina comprises the following steps:
mixing alkaline ternary precursor slurry and an aluminum salt solution for reaction, then carrying out aging and solid-liquid separation to obtain a ternary precursor with the surface coated with aluminum hydroxide, then mixing the ternary precursor with the surface coated with the aluminum hydroxide with a lithium source, sintering the mixed material, and obtaining the ternary material with the surface coated with the aluminum oxide after sintering.
Compared with the existing method for coating the ternary material finished product with the aluminum oxide, the method disclosed by the invention has the advantages that the ternary material with the surface coated with the aluminum oxide is obtained by coating the aluminum hydroxide on the surface of the ternary precursor and mixing the ternary precursor with the lithium source for primary sintering, the drying process and the secondary sintering process of the existing coating method are omitted, the process flow is shortened, the coating process is controlled simply, the equipment investment cost and the energy consumption cost are greatly saved, and the production efficiency is improved.
In addition, in the existing coating technology for obtaining the coating material by adding the uncoated ternary material into the liquid-phase coating agent for dispersion, drying and calcining, the coating material is difficult to be uniformly coated on the surface of the material through emulsification and dispersion, and the ternary material and the coating material Al are difficult to be avoided in the drying process2O3Resulting in Al of the surface of the ternary material2O3The coating is not uniform. The surface of the invention is uniformly coated with Al (OH)3The ternary precursor and a lithium source are mixed and sintered at one time, and part of Al is diffused into crystal grains on the surface of the material through high-temperature sintering to form a layer of uniform and compact Al2O3The coating layer and the particle surface layer contain a gradient doping material of a solid solution layer with Al doping concentration gradient, so that the ternary content can be effectively reduced in the charging and discharging process of the batteryThe direct contact area between the surface of the material and the electrolyte reduces the occurrence of side reactions, forms a thinner SEI film and consumes less Li+The surface layer of Al is doped in a gradient way to stabilize the material structure, and two aspects of beneficial improvement are combined to obviously improve the thermodynamic stability, the cycling stability and the safety performance of the ternary material. The performance test of the ternary material prepared by the invention shows that the beneficial effects are obvious.
Further, the alkaline ternary precursor slurry and an aluminum salt solution are simultaneously pumped into a reaction pipeline to be mixed, wherein hydroxyl ions and aluminum ions react to generate an aluminum hydroxide layer covering the surface of the ternary precursor;
the two ends of the reaction pipeline are respectively provided with a slurry inlet and a slurry outlet, the pipe wall of the reaction pipeline is provided with a plurality of feed inlets, and a plurality of baffles are arranged in the pipe; and the ternary precursor slurry enters the reaction pipeline from the slurry inlet, the aluminum salt solution enters the reaction pipeline from the plurality of feed inlets to be mixed with the ternary precursor slurry, and the mixed and reacted slurry is discharged from the slurry outlet.
The reaction pipeline is utilized to finish the preparation of Al (OH) on the surface of the ternary precursor3The step of coating, reaction tube's equipment cost is with low costs, and easy equipment can combine into the three process of mixing, reaction, transportation material and high-efficient the completion in an equipment, has improved production efficiency greatly, and the flow direction of the steerable thick liquids of a plurality of feed inlets and the baffle of this reaction tube is favorable to homogeneous mixing and abundant reaction.
Furthermore, the reaction pipeline is provided with 10-20 uniformly distributed feeding holes at intervals, and the baffle is a fan-shaped baffle. The integral structure of the reaction pipeline can ensure that the ternary precursor slurry and the aluminum salt solution are fully dispersed and mixed in the reaction pipeline, thereby being convenient for effectively controlling the reaction and controlling Al (OH)3The thickness of the coating layer is favorable for forming uniform Al (OH) on the surface of the ternary precursor3And (4) coating.
Further, the method specifically comprises the following steps:
(1) preparing soluble salts of nickel, cobalt and manganese and water into a mixed salt solution with the total metal ion concentration of 1-2mol/L for later use, preparing a sodium hydroxide solution with the mass concentration of 12-32% for later use, preparing an ammonia water solution with the mass concentration of 20-30% for later use, and preparing aluminum sulfate, aluminum nitrate or aluminum chloride and water into an aluminum salt solution with the aluminum ion concentration of 0.2-1mol/L for later use according to the molar ratio of nickel, cobalt and manganese of 5-9:1-4: 0-3;
(2) adding the mixed salt solution, ammonia water and sodium hydroxide solution into a reaction kettle, stirring for reaction, controlling the pH value of a reaction system to be 10.5-12, controlling the reaction temperature to be 45-65 ℃, introducing nitrogen into the reaction kettle, and reacting to obtain alkaline ternary precursor slurry;
(3) pumping alkaline ternary precursor slurry and aluminum salt solution into a reaction pipeline simultaneously for mixing, aging the obtained slurry for 1-3 hours after full reaction, washing the slurry with pure water after aging until the pH value of washing water is less than 8, and drying the slurry to obtain a ternary precursor with the surface coated with aluminum hydroxide;
(4) mixing a ternary precursor with the surface coated with aluminum hydroxide with a lithium source according to the molar ratio of the total amount of nickel, cobalt and manganese to lithium of 1:1-1.05, and then feeding the mixed material into a sintering furnace for sintering, wherein oxygen is introduced into the furnace during sintering;
(5) and mechanically crushing the sintered material, and sieving and demagnetizing to obtain the ternary material with the surface coated with the alumina.
Further, the step (2) is specifically as follows: firstly adding 3000L of 2000-plus-2000L of mixed salt solution as a base solution into a 5-cubic reaction kettle, then continuously adding 400L/h of mixed salt solution with the flow rate of 300-plus-400L/h, adjusting the pH value of the reaction system to be 10.5-12 by adding ammonia water and sodium hydroxide solution, and controlling ammonia molecules (NH) in the reaction system3) The total content of the alkaline ternary precursor slurry is 6-12g/L, the content of hydroxyl ions is 1-3g/L, the reaction temperature is controlled to be 45-65 ℃, and the alkaline ternary precursor slurry obtained by the reaction overflows from the reaction kettle to an aging kettle and is collected.
Further, in the step (2), the stirring speed in the reaction kettle is controlled at 180-260rpm, and the particle size of the slurry in the reaction kettle is adjusted to 9-13 μm.
Further, the step (3) is specifically: pumping alkaline ternary precursor slurry into a reaction pipeline from a slurry inlet, pumping aluminum salt solution into the reaction pipeline from a plurality of feed inlets to be mixed with the ternary precursor slurry, wherein the flow of the aluminum salt solution in each feed inlet is equal, discharging the obtained slurry into an aging kettle from a slurry outlet of the reaction pipeline after full reaction, aging for 2 hours, washing the slurry by using pure water for a centrifuge until the pH value of washing water is less than 8, removing dry water, and drying the dehydrated material in a dryer to obtain the ternary precursor with the surface coated with aluminum hydroxide.
Further, in the step (3), the flow rate of the ternary precursor slurry in the reaction pipeline is 300-600L/h, and the flow rate of the aluminum salt solution in each feed inlet is 0.5-2L/h.
Further, in the step (4), the sintering is: the temperature is maintained at 400 ℃ and 600 ℃ for 3-5 hours, and then at 700 ℃ and 950 ℃ for 8-14 hours.
The invention also provides the ternary material with the surface coated with the aluminum oxide, which is prepared by the preparation method.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic view of a reaction tube;
FIG. 2 is a schematic view of the structure of a subduct;
FIG. 3 is a schematic view taken along direction A in FIG. 2;
FIG. 4 is a micro-topography of the ternary material obtained in example 1;
FIG. 5 is a scanning spectrum of the nickel element and the aluminum element on the surface of the ternary material obtained in example 1;
FIG. 6 is a microscopic morphology of the ternary material obtained in comparative example 1.
Detailed Description
The preparation method of the ternary material with the surface coated with the aluminum oxide comprises the following steps:
and simultaneously pumping the alkaline ternary precursor slurry and an aluminum salt solution into a reaction pipeline for mixing reaction, then performing aging and solid-liquid separation to obtain a ternary precursor with the surface coated with aluminum hydroxide, mixing the ternary precursor with the surface coated with the aluminum hydroxide with a lithium source, sintering the mixed material, and sintering to obtain the ternary material with the surface coated with the aluminum oxide.
Referring to fig. 1-3, fig. 1 is a schematic diagram of a reaction pipeline, fig. 2 is a schematic diagram of a sub-pipeline, and fig. 3 is a schematic diagram of a direction a in fig. 2.
The reaction pipeline is formed by serially assembling 10-20 sections of sub-pipelines 1 through flanges 2, specifically, the reaction pipeline is formed by serially connecting 20 sections of sub-pipelines 1, and a slurry inlet 3 and a slurry outlet 4 are respectively arranged at two ends of the reaction pipeline.
The pipe wall in the middle of each section of the sub-pipe 1 is provided with a feeding hole 10, and the reaction pipe is provided with 20 feeding holes 10 which are uniformly distributed at intervals. The feed inlet 10 is connected with an inlet pipe 11, the one end of inlet pipe 11 stretches into in the subduct 1, the other end stretches out outside the subduct 1.
The inside of each section of subduct 1 is equipped with 5 fan-shaped baffles 12, 5 fan-shaped baffles 12 are evenly distributed along the length direction interval of subduct 1. The arc edge of each sector baffle 12 is matched and fixedly connected with the upper part or the lower part of the inner wall of the subduct 1.
Alkaline ternary precursor slurry enters the reaction pipeline from the slurry inlet 3, aluminum salt solution enters the reaction pipeline from the plurality of feed inlets 10 to be mixed with the ternary precursor slurry, and the slurry after the mixing reaction is discharged from the slurry outlet 4.
Example 1
In this example, a ternary material with an alumina-coated surface is prepared by the following steps:
(1) according to the molar ratio of Ni, Co and Mn to 6:2:2, soluble salts of nickel, cobalt and manganese and water are prepared into mixed salt solution with the total concentration of metal ions of 1-2mol/L for standby, sodium hydroxide solution with the mass concentration of 24% is prepared for standby, ammonia water solution with the mass concentration of 25% is prepared for standby, and aluminum sulfate, aluminum nitrate or aluminum chloride and water are prepared into aluminum salt solution with the concentration of aluminum ions of 0.2-1mol/L for standby.
(2) 2500L of mixed salt solution is added into a high-efficiency closed synthesis reaction kettle (the specification is 5 cubic meters) to be used as base solution, then the mixed salt solution with the flow rate of 360L/h is continuously added, and simultaneously, ammonia water and sodium hydroxide solution are added, and the reaction is carried out under stirring.
The pH value of the reaction system is adjusted to be maintained at 11.6 by controlling the amount of the added ammonia water and sodium hydroxide solution, the content of ammonia molecules in the reaction system is controlled to be 8g/L, the content of hydroxyl ions is controlled to be 2g/L, the reaction temperature is controlled to be 60 ℃, the stirring speed in the reaction kettle is controlled to be 220rpm, and nitrogen is introduced into the reaction kettle.
When the granularity D of the slurry in the reaction kettle50When the particle size reaches 10 mu m, the pH value of the reaction system and the stirring speed in the reaction kettle are finely adjusted, and the particle size of the slurry in the reaction kettle is controlled to be maintained at 10-11 mu m.
The reaction is continuous, and after the reaction is finished, the obtained alkaline ternary precursor slurry overflows from the reaction kettle to the first aging kettle and is collected.
(3) Pumping alkaline ternary precursor slurry in the first aging kettle into a reaction pipeline from a slurry inlet, and simultaneously pumping aluminum salt solution into the reaction pipeline from 20 feed inlets respectively to be mixed with the ternary precursor slurry, wherein the flow rate of the ternary precursor slurry in the reaction pipeline is 500L/h, and the flow rate of the aluminum salt solution in each feed inlet is 1L/h. And reacting hydroxyl ions in the mixed slurry in the reaction pipeline with aluminum ions to generate an aluminum hydroxide layer covering the surface of the ternary precursor.
And after full reaction, discharging the obtained slurry into a second aging kettle from a slurry outlet of the reaction pipeline, aging for 2 hours, washing the aged slurry by using pure water for a centrifuge according to the proportion of 1 ton of solid material to 11 tons of pure water until the pH value of washing water is less than 8, removing water, and drying the dehydrated material in a dryer to obtain the ternary precursor with the surface coated with aluminum hydroxide.
(4) Firstly, screening a ternary precursor coated with aluminum hydroxide on the surface by a 200-mesh sieve, then adding the screened ternary precursor and a lithium source into a high-speed mixer according to the molar ratio of (Ni + Co + Mn) to Li being 1:1.03, mixing, then filling the mixed material into a sagger, and then feeding into a sintering furnace for sintering, wherein the sintering heat preservation curve is as follows: the temperature is preserved for 4 hours at 400 ℃ and then preserved for 12 hours at 870 ℃, and oxygen with the purity of 95 percent is introduced into the furnace during sintering.
(5) And naturally cooling the sintered material, mechanically crushing and grinding the material, sieving the material by using a 300-mesh sieve, and demagnetizing the material to obtain the ternary material with the surface coated with the alumina.
Referring to fig. 4-5, fig. 4 is a micro-topography of the ternary material obtained in the present embodiment, and fig. 5 is a scanning energy spectrum of nickel (Ni) and aluminum (Al) elements obtained by analyzing the surface of the ternary material obtained in the present embodiment with a material spectrometer.
As can be seen from FIG. 4, the ternary material particles obtained in this example are dense on the surface, which shows that the alumina layer is uniformly coated.
The aluminum (Al) content of the ternary material obtained in this example was determined to be about 2800 ppm.
The ternary material obtained in the embodiment is made into a button cell, and an electrical property test is carried out under the test voltage of 3-4.3V, and the test result is as follows: under the discharge rate of 1C, the specific discharge capacity of the ternary material is 165mAh/g, and the retention rate of the 1C 100-time charge-discharge capacity is 98%.
Comparative example 1
The comparative example prepares a ternary material with the surface not coated with alumina by the following steps:
(1) according to the molar ratio of Ni, Co and Mn to 6:2:2, soluble salts of nickel, cobalt and manganese and water are prepared into mixed salt solution with the total concentration of metal ions of 1-2mol/L for later use, sodium hydroxide solution with the mass concentration of 24% is prepared for later use, and ammonia water solution with the mass concentration of 25% is prepared for later use.
(2) 2500L of mixed salt solution is added into a high-efficiency closed synthesis reaction kettle (the specification is 5 cubic meters) to be used as base solution, then the mixed salt solution with the flow rate of 360L/h is continuously added, and simultaneously, ammonia water and sodium hydroxide solution are added, and the reaction is carried out under stirring.
The pH value of the reaction system is adjusted to be maintained at 11.6 by controlling the amount of the added ammonia water and sodium hydroxide solution, the total content of ammonia molecules in the reaction system is controlled to be 8g/L, the content of hydroxyl ions is 2g/L, the reaction temperature is controlled to be 60 ℃, the stirring speed in the reaction kettle is controlled to be 220rpm, and nitrogen is introduced into the reaction kettle.
When the granularity D of the slurry in the reaction kettle50When the pH value of the reaction system reaches 10 mu m, the pH value and the reaction ratio of the reaction system are adjustedThe stirring speed in the reaction kettle is controlled, and the granularity of the slurry in the reaction kettle is maintained at 10-11 mu m.
The reaction is continuous, after the reaction is finished, the obtained ternary precursor slurry overflows from the reaction kettle to the aging kettle and is collected, and then the aging is carried out for 2 hours. And according to the proportion of 1 ton of solid material to 11 tons of pure water, washing the aged slurry by using pure water for a centrifuge until the pH value of washing water is less than 8, then removing water, and sending the dehydrated material into a dryer for drying to obtain the ternary precursor.
(3) Firstly, screening a ternary precursor by a 200-mesh sieve, then adding the screened ternary precursor and a lithium source into a high-speed mixer according to the molar ratio of (Ni + Co + Mn) to Li being 1:1.03 for mixing, then loading the mixed material into a sagger, and then feeding the sagger into a sintering furnace for sintering, wherein the sintering heat preservation curve is as follows: the temperature is preserved for 4 hours at 400 ℃ and then preserved for 12 hours at 870 ℃, and oxygen with the purity of 95 percent is introduced into the furnace during sintering.
(4) And naturally cooling the sintered material, mechanically crushing and grinding the material, sieving the material by using a 300-mesh sieve, and demagnetizing the material to obtain the ternary material of which the surface is not coated with the alumina.
Referring to fig. 6, fig. 6 is a micro-topography of the ternary material obtained in the present comparative example.
As can be seen from the figure, the ternary material particles obtained in the comparative example have loose and rough surfaces without being coated with the alumina layer.
The ternary material obtained in the comparative example is prepared into a button cell, and the electrical property test is carried out under the test voltage of 3-4.3V, and the test result is as follows: under the discharge rate of 1C, the specific discharge capacity of the ternary material is 165mAh/g, and the retention rate of the 1C 100-time charge-discharge capacity is 92%.
Comparing the ternary material obtained in example 1 with that obtained in comparative example 1, the ternary material with the surface coated with the alumina prepared by the invention has higher structural stability, and higher charge-discharge performance reliability, cycle stability and safety performance.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (9)
1. A preparation method of a ternary material with the surface coated with alumina is characterized by comprising the following steps: the method comprises the following steps:
mixing alkaline ternary precursor slurry with an aluminum salt solution for reaction, then carrying out aging and solid-liquid separation to obtain a ternary precursor with the surface coated with aluminum hydroxide, then mixing the ternary precursor with the surface coated with the aluminum hydroxide with a lithium source, sintering the mixed material, and obtaining a ternary material with the surface coated with aluminum oxide after sintering; the alkaline ternary precursor slurry and an aluminum salt solution are simultaneously pumped into a reaction pipeline to be mixed, and hydroxyl ions and aluminum ions react to generate an aluminum hydroxide layer covering the surface of the ternary precursor; the two ends of the reaction pipeline are respectively provided with a slurry inlet and a slurry outlet, the pipe wall of the reaction pipeline is provided with a plurality of feed inlets, and a plurality of baffles are arranged in the pipe; and the ternary precursor slurry enters the reaction pipeline from the slurry inlet, the aluminum salt solution enters the reaction pipeline from the plurality of feed inlets to be mixed with the ternary precursor slurry, and the mixed and reacted slurry is discharged from the slurry outlet.
2. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 1, wherein the method comprises the following steps: the reaction pipeline is provided with 10-20 uniformly distributed feeding holes at intervals, and the baffle is a fan-shaped baffle.
3. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 2, wherein the method comprises the following steps: the method specifically comprises the following steps:
(1) preparing soluble salts of nickel, cobalt and manganese and water into a mixed salt solution with the total metal ion concentration of 1-2mol/L for later use, preparing a sodium hydroxide solution with the mass concentration of 12-32% for later use, preparing an ammonia water solution with the mass concentration of 20-30% for later use, and preparing aluminum sulfate, aluminum nitrate or aluminum chloride and water into an aluminum salt solution with the aluminum ion concentration of 0.2-1mol/L for later use according to the molar ratio of nickel, cobalt and manganese of 5-9:1-4: 0-3;
(2) adding the mixed salt solution, ammonia water and sodium hydroxide solution into a reaction kettle, stirring for reaction, controlling the pH value of a reaction system to be 10.5-12, controlling the reaction temperature to be 45-65 ℃, introducing nitrogen into the reaction kettle, and reacting to obtain alkaline ternary precursor slurry;
(3) pumping alkaline ternary precursor slurry and aluminum salt solution into a reaction pipeline simultaneously for mixing, aging the obtained slurry for 1-3 hours after full reaction, washing the slurry with pure water after aging until the pH value of washing water is less than 8, and drying the slurry to obtain a ternary precursor with the surface coated with aluminum hydroxide;
(4) mixing a ternary precursor with the surface coated with aluminum hydroxide with a lithium source according to the molar ratio of the total amount of nickel, cobalt and manganese to lithium of 1:1-1.05, and then feeding the mixed material into a sintering furnace for sintering, wherein oxygen is introduced into the furnace during sintering;
(5) and mechanically crushing the sintered material, and sieving and demagnetizing to obtain the ternary material with the surface coated with the alumina.
4. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 3, wherein the method comprises the following steps: the step (2) is specifically as follows: firstly adding 3000L of 2000-plus-one mixed salt solution into a 5-cubic reaction kettle as a base solution, then continuously adding 400L/h of the mixed salt solution with the flow rate of 300-plus-one, adjusting the pH value of the reaction system to be 10.5-12 by adding ammonia water and sodium hydroxide solution, controlling the total content of ammonia molecules in the reaction system to be 6-12g/L, the content of hydroxide ions to be 1-3g/L, controlling the reaction temperature to be 45-65 ℃, and overflowing the alkaline ternary precursor slurry obtained by the reaction from the reaction kettle to an aging kettle for collection.
5. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 4, wherein the method comprises the following steps: in the step (2), the stirring speed in the reaction kettle is controlled at 180-260rpm, and the granularity of the slurry in the reaction kettle is adjusted to 9-13 μm.
6. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 3, wherein the method comprises the following steps: the step (3) is specifically as follows: pumping alkaline ternary precursor slurry into a reaction pipeline from a slurry inlet, pumping aluminum salt solution into the reaction pipeline from a plurality of feed inlets to be mixed with the ternary precursor slurry, wherein the flow of the aluminum salt solution in each feed inlet is equal, discharging the obtained slurry into an aging kettle from a slurry outlet of the reaction pipeline after full reaction, aging for 2 hours, washing the slurry by using pure water for a centrifuge until the pH value of washing water is less than 8, removing dry water, and drying the dehydrated material in a dryer to obtain the ternary precursor with the surface coated with aluminum hydroxide.
7. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 6, wherein the method comprises the following steps: in the step (3), the flow rate of the ternary precursor slurry in the reaction pipeline is 300-600L/h, and the flow rate of the aluminum salt solution in each feed inlet is 0.5-2L/h.
8. The method for preparing the ternary material with the surface coated with the aluminum oxide according to claim 3, wherein the method comprises the following steps: in the step (4), the sintering is as follows: the temperature is maintained at 400 ℃ and 600 ℃ for 3-5 hours, and then at 700 ℃ and 950 ℃ for 8-14 hours.
9. The ternary material with the surface coated with the alumina, which is prepared by the preparation method of any one of claims 1 to 8.
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| US10913885B1 (en) * | 2019-07-18 | 2021-02-09 | Halliburton Energy Services, Inc. | Metal that hydrates in wellbore fluid and creates an expanding cement |
| CN113809297B (en) * | 2021-09-08 | 2024-02-02 | 深圳石墨烯创新中心有限公司 | Preparation method of ternary positive electrode material precursor with multilevel structure |
| CN113903884B (en) * | 2021-09-30 | 2022-07-22 | 清华大学深圳国际研究生院 | Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery |
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