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CN-117480269-B - Method for recovering retired lithium battery step by step

CN117480269BCN 117480269 BCN117480269 BCN 117480269BCN-117480269-B

Abstract

The invention provides a step-by-step recycling method of retired lithium batteries, which comprises the following steps of preprocessing the retired lithium batteries to obtain powder, mixing the powder with first organic acid, carrying out leaching reaction to obtain a leaching solution containing lithium and aluminum and first leaching slag, mixing the first leaching slag with a compound ammonia source, carrying out leaching reaction to obtain a copper-containing leaching solution and second leaching slag, carrying out acid leaching on the second leaching slag to obtain a nickel-containing solution, cobalt-containing solution, manganese-containing solution, iron-containing solution and third leaching slag, mixing the nickel-containing solution, cobalt-containing solution, manganese-containing solution, iron-containing solution and pH value regulator, carrying out reaction, and aging to obtain a nickel-containing solution, cobalt-containing solution, manganese-containing solution and iron-precipitating slag. The method reduces the loss of valuable metal elements lithium, nickel, cobalt and manganese and the output of slag quantity, improves the recovery rate of the metal lithium, and the high-value utilization of copper and aluminum in the leaching solution, reduces the production cost of the process, and realizes the recycling and reduction of solid wastes in the wet recovery process of the lithium battery.

Inventors

  • DENG BIN
  • QIU YALI
  • LIU YONGQI
  • Gong Qinxue
  • LI CHANGDONG

Assignees

  • 广东邦普循环科技有限公司
  • 湖南邦普循环科技有限公司

Dates

Publication Date
20260505
Application Date
20230904

Claims (20)

  1. 1. A method for progressively recycling retired lithium batteries, the method comprising the steps of: (1) Pretreating the retired lithium battery to obtain powder; (2) Mixing the powder with a first organic acid, and carrying out leaching reaction to obtain leaching solution containing lithium and aluminum and first leaching slag, and extracting more than 98% of lithium element and dissolving 100% of aluminum; (3) Mixing the first leaching residue with a composite ammonia source, and carrying out leaching reaction to obtain a copper-containing leaching solution and a second leaching residue; (4) Acid leaching is carried out on the second leaching slag to obtain a solution containing nickel, cobalt, manganese and iron and a third leaching slag; the specific step of acid leaching in the step (4) comprises the steps of mixing the second leaching residue with sulfuric acid solution for acid leaching reaction; after the second leaching residue is mixed with the sulfuric acid solution, reducing gas is also introduced into the mixed solution; (5) Mixing the nickel-containing, cobalt-containing, manganese-containing and iron solution with a pH value regulator, reacting, and aging to obtain a nickel-containing, cobalt-containing and manganese-containing solution and iron-precipitating slag; The first organic acid in the step (2) comprises any one or a combination of at least two of oxalic acid, tartaric acid, malic acid and acetic acid; the concentration of the first organic acid in the step (2) is 0.5-0.6mol/L; The mass volume ratio of the powder material to the first organic acid in the step (2) is 1g (6-10) mL; carrying out aluminum precipitation treatment on the lithium-containing aluminum leaching solution obtained in the step (2), wherein the specific steps comprise: Mixing the lithium-containing leaching solution, the aluminum leaching solution and the second organic acid, carrying out a complex reaction, and aging to obtain a lithium-containing leaching solution and an aluminum salt; the second organic acid comprises phytic acid; The molar ratio of Al ions to phytic acid in the leaching solution containing lithium and aluminum is (2-4): 1; the compound ammonia source in the step (3) comprises ammonia water and an ammonium chloride solution; the concentration of the ammonia water is 4-5mol/L; The concentration of the ammonium chloride solution is 5-6.5mol/L; The volume ratio of the ammonia water to the ammonium chloride solution is (15-25) (5-15); The mass volume ratio of the first leaching residue to the compound ammonia source in the step (3) is 1g (5-10) mL; After the nickel, cobalt, manganese and iron containing solution and the pH value regulator are mixed in the step (5), the pH value of the mixed solution is 3-3.5; The temperature of the reaction in the step (5) is 75-95 ℃.
  2. 2. The process of claim 1, wherein the powder of step (1) has a particle size D50 of 48-78 μm.
  3. 3. The method of claim 1, wherein the step of preprocessing comprises: discharging, crushing, calcining and sieving the retired lithium battery.
  4. 4. The process of claim 1, wherein the concentration of the first organic acid of step (2) is 0.5-0.55mol/L.
  5. 5. The process of claim 1, wherein the mass to volume ratio of the powder of step (2) to the first organic acid is 1g (7-8) mL.
  6. 6. The method of claim 1, wherein the temperature of the leaching reaction of step (2) is 50-80 ℃.
  7. 7. The method of claim 1, wherein the temperature of the leaching reaction of step (2) is 55-65 ℃.
  8. 8. The method of claim 1, wherein the time of the leaching reaction of step (2) is 40-80min.
  9. 9. The method of claim 1, wherein the leaching reaction of step (2) takes 50-70 minutes.
  10. 10. The method of claim 1, wherein after the leaching reaction in step (2) is finished, the obtained filter residue is washed and filtered to obtain a first leaching residue and a filtrate, and the filtrate is mixed with a reaction solution obtained by the leaching reaction to obtain a leaching solution containing lithium and aluminum.
  11. 11. The method according to claim 1, wherein the molar ratio of Al ions to phytic acid in the lithium-containing and aluminum-containing leaching solution is (3-3.5): 1.
  12. 12. The method of claim 1, wherein the temperature of the complexation reaction is 50-70 ℃.
  13. 13. The method of claim 1, wherein the temperature of the complexation reaction is 55-65 ℃.
  14. 14. The method of claim 1, wherein the time of the complexation reaction is 20-50min.
  15. 15. The method of claim 1, wherein the aging time is 30-60 minutes.
  16. 16. The method of claim 1, wherein the aging time is 50-60 minutes.
  17. 17. The method of claim 1, wherein the aluminum salt comprises an aluminum-containing phytate.
  18. 18. The method of claim 1, wherein the aluminum salt is heat treated to yield aluminum metaphosphate.
  19. 19. The method of claim 18, wherein the temperature of the heat treatment is 800-1000 ℃.
  20. 20. The method of claim 18, wherein the temperature of the heat treatment is 900-1000 ℃.

Description

Method for recovering retired lithium battery step by step Technical Field The disclosure belongs to the technical field of lithium ion battery recovery, and particularly relates to a step-by-step recovery method of retired lithium batteries. Background With the rapid development of new energy industry, the full life cycle regeneration industry of retired lithium batteries is vigorous, in the existing lithium battery cycle regeneration technology, retired lithium batteries are fully discharged in a physical and chemical mode, then components such as battery powder, pole pieces (aluminum foil, copper foil) and diaphragms are directly disassembled, calcined and screened, and then relatively pure ternary slurry and lithium-containing feed liquid are obtained through a series of processes such as acid leaching, impurity removal and extraction. For this reason, some solutions are proposed in the prior art, for example CN106191466a discloses a method for recovering lithium from waste lithium iron phosphate batteries, which comprises the steps of disassembling the waste lithium iron phosphate batteries to obtain battery winding cores, calcining the battery winding cores, crushing the battery winding cores, sieving to obtain anode and cathode mixtures, adding alkali liquor into the anode and cathode mixtures to remove residual aluminum in the anode and cathode mixtures, filtering to obtain filter mud, leaching the filter mud with strong acid to remove carbon and ferric phosphate to obtain a leaching solution, adjusting the pH of the leaching solution to produce a small amount of precipitated iron, filtering to obtain a filtrate, removing copper impurities in the filtrate, filtering to obtain a filtrate, and adding solid sodium carbonate to the filtrate to obtain lithium carbonate precipitate. CN113285135A discloses a multi-component recycling method of waste lithium iron phosphate batteries, which comprises the steps of breaking shells of the waste lithium iron phosphate batteries after discharge treatment, separating, treating battery cores to obtain solvent recycling liquid, crushing and sorting the battery cores to obtain lithium iron phosphate coarse powder, copper powder and aluminum powder, adding the lithium iron phosphate coarse powder into acid liquor for reaction, filtering to obtain acid leaching liquid and carbon residue, washing and drying the carbon residue to obtain high-carbon graphite, regulating the PH value of the acid leaching liquid, adding a reducing agent for copper removal, filtering to obtain copper removal liquid and copper residue, adding an oxidizing agent and a proper amount of phosphorus source into the copper removal liquid to obtain ferric orthophosphate, adding an alkaline solution into the iron precipitation liquid to obtain aluminum removal liquid and aluminum residue, adding the alkaline solution into the aluminum precipitation liquid to obtain alkaline solution and alkaline residue, evaporating and concentrating the alkaline solution to obtain lithium-rich solution, and adding the lithium carbonate solution into sodium carbonate solution. However, the loss of valuable metal elements in the solution is still not small, and the production cost of the process is high. Therefore, how to efficiently reduce the loss of valuable metal elements in the recovery process and reduce the production cost of the process is a problem to be solved currently. Disclosure of Invention The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims. The invention aims to provide a method for recycling retired lithium batteries step by step. The method reduces the loss of valuable metal elements lithium, nickel, cobalt and manganese and the output of slag quantity, improves the recovery rate of the metal lithium, and the high-value utilization of copper and aluminum in the leaching solution, reduces the production cost of the process, and realizes the recycling and reduction of solid wastes in the wet recovery process of the lithium battery. In order to achieve the purpose of the disclosure, the following technical scheme is adopted in the disclosure: In a first aspect, the present disclosure provides a method for progressive recovery of retired lithium batteries, the method comprising the steps of: (1) Pretreating the retired lithium battery to obtain powder; (2) Mixing the powder with a first organic acid, and carrying out leaching reaction to obtain a leaching solution containing lithium and aluminum and a first leaching residue; (3) Mixing the first leaching residue with a composite ammonia source, and carrying out leaching reaction to obtain a copper-containing leaching solution and a second leaching residue; (4) Acid leaching is carried out on the second leaching slag to obtain a solution containing nickel, cobalt, manganese and iron and a third leaching slag; (5) And mixing the nickel, cobalt, manganese and iron solutio