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CN-119633420-B - Spray pyrolysis device and method for preparing ternary positive electrode precursor by adopting same

CN119633420BCN 119633420 BCN119633420 BCN 119633420BCN-119633420-B

Abstract

The invention discloses a spray pyrolysis device and a method for preparing ternary anode precursors by using the same. The spray pyrolysis device comprises a feeding unit, a spraying unit and a pyrolysis unit, wherein a first unit, a second unit and a third unit are sequentially arranged in a cavity of the spraying unit, an atomization device is arranged at an outlet of the third unit, the first unit, the second unit and the third unit are respectively heated through a first ultrasonic wave generating assembly, a second ultrasonic wave generating assembly and a third ultrasonic wave generating assembly, the atomization device is communicated with the pyrolysis unit, atomized liquid generated by the atomization device enters the pyrolysis unit, an ignition device is arranged at an inlet of the pyrolysis unit, and P 1 <P 2 <P 3 is arranged at an inlet of the pyrolysis unit. The spray pyrolysis device can avoid the problems of particle crushing and hollowing of the precursor of the positive electrode material, so that the precursor of the positive electrode material has high tap density, low specific surface area and low chloride content, thereby improving the energy density, the cycle performance and the safety performance of the positive electrode material and reducing the preparation cost.

Inventors

  • XU KAIHUA
  • BIAN DI
  • ZHANG KUN
  • LI CONG
  • SUN ZHAOJIAN
  • YUAN NING

Assignees

  • 荆门市格林美新材料有限公司
  • 格林美股份有限公司

Dates

Publication Date
20260508
Application Date
20241212

Claims (20)

  1. 1. A method for preparing a ternary positive electrode precursor by using a spray pyrolysis device, which is characterized by comprising the following steps: (1) The method comprises the steps of feeding a chloride salt solution of a ternary positive electrode precursor to a spraying unit through a feeding unit, and heating the chloride salt solution by the ultrasonic action of the spraying unit, wherein the temperatures of a first unit, a second unit and a third unit in a cavity of the spraying unit are sequentially increased to obtain a heated chloride salt solution; (2) Atomizing the heated chloride salt solution by using an atomizing device to obtain atomized liquid; (3) Starting an ignition device, igniting the atomized liquid, and performing pyrolysis to obtain a ternary positive electrode precursor; The initial discharge capacity of the battery assembled by the ternary positive electrode precursor material prepared by the method is more than or equal to 205.5mAh/g; the spray pyrolysis device comprises a feeding unit, a spraying unit and a pyrolysis unit; the device comprises a spray unit, a first ultrasonic generation assembly, a second ultrasonic generation assembly, a third ultrasonic generation assembly, an ignition device, a pyrolysis unit, a first unit, a second unit and a third unit, wherein the first unit, the second unit and the third unit are sequentially arranged in a cavity of the spray unit, an atomization device is arranged at an outlet of the third unit, the first unit, the second unit and the third unit are respectively heated through the first ultrasonic generation assembly, the second ultrasonic generation assembly and the third ultrasonic generation assembly, the atomization device is communicated with the pyrolysis unit, so that atomized liquid generated by the atomization device enters the pyrolysis unit, and the ignition device is arranged at an inlet of the pyrolysis unit; The atomizing device is an ultrasonic oscillation atomizer; The output power of the ultrasonic generator in the first ultrasonic wave generating assembly is P 1 , the output power of the ultrasonic generator in the second ultrasonic wave generating assembly is P 2 , and the output power of the ultrasonic generator in the first ultrasonic wave generating assembly is P 3 ,P 1 < P 2 < P 3 .
  2. 2. The method of claim 1, wherein the first ultrasonic wave generating assembly comprises at least 2 ultrasonic wave generators symmetrically disposed along a circumferential direction of the cavity.
  3. 3. The method of claim 1, wherein the first ultrasonic wave generating assembly has the same spacing of ultrasonic wave generators.
  4. 4. The method of claim 1, wherein the second ultrasonic wave generating assembly comprises at least 2 ultrasonic wave generators symmetrically disposed along a circumferential direction of the cavity.
  5. 5. The method of claim 1, wherein the spacing of the ultrasonic generators in the second ultrasonic generating assembly is the same.
  6. 6. The method of claim 1, wherein the third ultrasonic wave generating assembly comprises at least 2 ultrasonic wave generators symmetrically disposed along a circumferential direction of the cavity.
  7. 7. The method of claim 1, wherein the third ultrasonic wave generating assembly has the same pitch of ultrasonic wave generators.
  8. 8. The method according to claim 1, wherein the feed unit is adapted to store and supply a salt solution to the spray unit.
  9. 9. The method of claim 1, wherein the spray pyrolysis apparatus further comprises a dechlorination device, an inlet of the dechlorination device being in communication with an outlet of the pyrolysis unit.
  10. 10. The method of claim 1, wherein the chloride salt solution of the ternary positive electrode precursor comprises lithium salt, nickel chloride, cobalt chloride, and manganese chloride, wherein the ratio of the molar amount of lithium element to the total molar amount of nickel element, cobalt element, and manganese element is (1-1.1): 1.
  11. 11. The method of claim 10, wherein the lithium salt is at least one of lithium nitrate, lithium hydroxide, lithium nitrate, and lithium chloride.
  12. 12. The method of claim 11, wherein the lithium salt is lithium chloride.
  13. 13. The method according to claim 1, characterized in that the feed liquid pressure of the atomizing device in the atomizing unit is 1bar-3bar.
  14. 14. The method of claim 1, wherein the liquid feed rate of the atomizing device in the atomizing unit is 0.1m3/h to 3.0m3/h.
  15. 15. The method according to claim 1, wherein the gas injection pressure of the atomizing means in the atomizing unit is 0.3MPa to 0.8MPa.
  16. 16. The method of claim 1, wherein the atomized liquid is carried into the pyrolysis unit by a carrier gas comprising at least one of dry compressed air, oxygen, or argon.
  17. 17. The method of claim 16, wherein the carrier gas has a flow rate of 40m3/h to 200m3/h.
  18. 18. The method of claim 1, wherein the temperature in the first unit is 50 ℃ to 200 ℃, the temperature in the second unit is 200 ℃ to 550 ℃, and the temperature in the third unit is 500 ℃ to 800 ℃.
  19. 19. The method of claim 1, wherein the output power P 1 of the first unit is 2.0kW-2.5kW, the output power P 2 of the second unit is 2.7kW-2.9kW, and the output power of the third unit is 3.0kW-4.0kW.
  20. 20. The method of claim 1, wherein the pyrolysis is at a temperature of 750 ℃ to 1200 ℃.

Description

Spray pyrolysis device and method for preparing ternary positive electrode precursor by adopting same Technical Field The invention belongs to the technical field of batteries, and relates to a spray pyrolysis device and a method for preparing a ternary positive electrode precursor by using the same. Background The lithium ion battery is widely applied to portable electronic equipment, electric tools, energy storage devices, electric vehicles and hybrid electric vehicles because of the advantages of high working potential, high specific energy, long cycle performance, no pollution and the like. However, with the continuous expansion of the usage scale of lithium ion batteries, the price of relevant raw materials is also higher and higher, and especially the price of relevant scarce resources is high. The rising price of raw materials must lead to the rising cost of the lithium ion battery, and further adversely affects the application of the lithium ion battery. Because the positive electrode material has a relatively high ratio in the overall battery cost, reducing the processing costs of the positive electrode material and the positive electrode material precursor is a key means of reducing the overall battery cost. Currently, a ternary positive electrode precursor is generally synthesized by adopting a coprecipitation method, the process of the method is complex, the time consumption is long, and a large amount of ammonia nitrogen wastewater is generated in the production process and needs to be treated, so that considerable environmental protection cost is brought. In contrast, the spray pyrolysis method for preparing the ternary positive electrode precursor is simpler in process and shorter in time. The hydrogen chloride gas generated by the method can be recycled after absorption treatment, so that the processing cost of the material is effectively reduced. The inventor finds that when acetate and nitrate are used as solutions to prepare the lithium ion positive electrode material by spray pyrolysis, the solubility of the acetate in water is low, the melting point of the nitrate is low, and the two solutions are easy to crust at the outer edges of atomized liquid drops in the spray pyrolysis process, so that secondary precursor particles are crushed or hollow, and the ternary material prepared by high-temperature calcination of the precursor has low tap density and high specific surface area, thereby having adverse effects on the energy density, the cycle performance and the safety performance of a battery, and generating toxic and harmful gas. Therefore, the strategy for preparing the positive electrode material precursor by spray pyrolysis is provided, the problems of particle breakage and hollowing of the positive electrode material precursor are avoided, the tap density of the positive electrode material precursor is high, the specific surface area is low, the chloride content is low, the energy density, the electrochemical performance and the safety performance of the positive electrode material are further improved, the preparation cost is reduced, and the technical problem to be solved urgently at present is solved. Disclosure of Invention The invention aims to solve the problems in the prior art and provide a spray pyrolysis device and a method for preparing a ternary positive electrode precursor by using the same. In order to achieve the above purpose, the invention adopts the following technical scheme: in a first aspect, the present invention provides a spray pyrolysis apparatus, characterized in that the spray pyrolysis apparatus comprises a feed unit, a spray unit and a pyrolysis unit; The device comprises a spraying unit, a first unit, a second unit and a third unit, wherein the first unit, the second unit and the third unit are sequentially arranged in a cavity of the spraying unit, an atomization device is arranged at an outlet of the third unit, the first unit, the second unit and the third unit are respectively heated through a first ultrasonic wave generating assembly, a second ultrasonic wave generating assembly and a third ultrasonic wave generating assembly, the atomization device is communicated with a pyrolysis unit, atomized liquid generated by the atomization device enters the pyrolysis unit, and an ignition device is arranged at an inlet of the pyrolysis unit; The output power of the ultrasonic generator in the first ultrasonic wave generating assembly is P 1, the output power of the ultrasonic generator in the second ultrasonic wave generating assembly is P 2, and the output power of the ultrasonic generator in the first ultrasonic wave generating assembly is P 3,P1<P2<P3. According to the spray pyrolysis device, the first unit, the second unit and the third unit are arranged in the cavity of the spray unit, ultrasonic is utilized for heating, the output power of the ultrasonic generators in the first unit, the second unit and the third unit is regulated and controlled, ult