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CN-117902639-B - Method for preparing nickel-cobalt-manganese ternary precursor and lithium carbonate from waste lithium ion battery anode powder

CN117902639BCN 117902639 BCN117902639 BCN 117902639BCN-117902639-B

Abstract

The invention relates to the field of waste lithium ion battery recovery, and discloses a method for preparing a nickel-cobalt-manganese ternary precursor and lithium carbonate by short-process regeneration of waste lithium ion battery positive electrode powder. The method comprises the steps of (1) mixing waste lithium ion battery anode powder with nitrilotriacetic acid solution and bicarbonate solution for leaching, obtaining leaching slag and leaching liquid after leaching, 2) pyrolyzing the leaching liquid obtained in the step (1), filtering to obtain lithium carbonate precipitate and pyrolyzed liquid, and 3) performing coprecipitation reaction on the pyrolyzed liquid obtained in the step (2) and sodium hydroxide solution to obtain a ternary precursor. The invention can realize preferential lithium extraction, reduce the loss of lithium and the influence on coprecipitation in the production process of the precursor, reduce the steps of nickel-cobalt-manganese separation and purification required in the original lithium extraction process and improve the lithium extraction efficiency.

Inventors

  • HU WENYANG
  • HUANG MIN
  • WANG JING

Assignees

  • 四川智汇新能源有限公司

Dates

Publication Date
20260505
Application Date
20240111

Claims (10)

  1. 1. The method for preparing the nickel-cobalt-manganese ternary precursor and the lithium carbonate by short-process regeneration of the waste lithium ion battery positive electrode powder is characterized by comprising the following steps of: (1) Mixing the anode powder of the waste lithium ion battery with nitrilotriacetic acid solution and bicarbonate solution for leaching, and obtaining leaching residues and leaching liquid after the leaching is completed; (2) Pyrolyzing the leaching solution obtained in the step (1), and filtering to obtain lithium carbonate precipitation and pyrolyzed solution; (3) And (3) performing coprecipitation reaction on the pyrolyzed liquid obtained in the step (2) and a sodium hydroxide solution to obtain a ternary precursor.
  2. 2. The method of claim 1, wherein in step (1), the nitrilotriacetic acid solution has a concentration of 1 to 10mol/L.
  3. 3. The method of claim 1, wherein in the step (1), the bicarbonate solution is sodium bicarbonate solution, and the concentration of the sodium bicarbonate solution is 1-3 mol/L.
  4. 4. The method of claim 3, wherein in step (1), the volume ratio of nitrilotriacetic acid solution to sodium bicarbonate solution is 1:1 to 5:1.
  5. 5. The method according to claim 1, wherein in the step (1), the leaching solid-to-liquid ratio of the positive electrode powder is 10 to 100g/L.
  6. 6. The method according to any one of claims 1 to 5, wherein in step (1), the leaching temperature is 30 to 90 ℃.
  7. 7. The method of any one of claims 1-5, wherein in step (2), the pyrolysis temperature of the leachate is 50-100 ℃.
  8. 8. The method according to claim 1, wherein in the sodium hydroxide solution in the step (3), the mass fraction of sodium hydroxide is 10-30%.
  9. 9. The method according to claim 1, wherein in the step (3), the pH of the reaction is controlled to be 10 to 12 during the coprecipitation reaction.
  10. 10. The method of claim 1, wherein in step (3), the time of the coprecipitation reaction is 5 to 20 hours.

Description

Method for preparing nickel-cobalt-manganese ternary precursor and lithium carbonate from waste lithium ion battery anode powder Technical Field The invention belongs to the field of waste lithium ion battery recovery, and particularly relates to a method for preparing a nickel-cobalt-manganese ternary precursor and lithium carbonate by short-process regeneration of waste lithium ion battery positive electrode powder. Background The waste lithium ion battery contains a large amount of harmful heavy metals and organic chemical substances, wherein the mass fraction of metal elements such as nickel, cobalt, manganese, lithium and the like can reach more than 20%. In order to reduce the influence of the waste lithium ion battery on the environment and solve the problem of scarcity of metal resources, the recovery of the waste lithium ion battery is urgent. The recycling process of the anode material of the waste lithium ion battery is more researched. The leaching method based on inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and the like has high leaching efficiency and stable process, but the leaching agent with high cost, the slow leaching process and the complex wastewater treatment greatly prevent the application of the leaching agent. In order to improve leaching rate and simplify process flow, researchers have proposed to take nitrate, sulfate, chloride and the like as roasting agents, leaching the lithium by a water leaching method after high-temperature roasting, and then recycling other metal elements by an acid leaching method. The core of the recovery method is that lithium is converted into soluble substances and separated from the rest elements, so that the recovery process is shortened. Although the process can achieve high-efficiency selective lithium extraction, metal ions in the roasting agent are usually transferred to an insoluble solid phase and need to be additionally treated, so that the recovery difficulty is increased and the treatment process is prolonged. Moreover, the above-mentioned processes all involve the use of ammonia water which has a pungent smell and is volatile, and the production process causes damage to the body and the environment of the operators. Disclosure of Invention The invention aims to provide a method for preparing a nickel-cobalt-manganese ternary precursor and lithium carbonate by short-process regeneration of waste lithium ion battery positive electrode powder, which can realize preferential lithium extraction and is environment-friendly in production process. In order to achieve the purpose of the invention, the specific technical scheme is as follows: A method for preparing a nickel-cobalt-manganese ternary precursor and lithium carbonate by short-process regeneration of waste lithium ion battery positive electrode powder comprises the following steps: (1) Mixing the anode powder of the waste lithium ion battery with nitrilotriacetic acid (NTA) solution and bicarbonate solution for leaching to obtain leaching residues and leaching liquid after leaching; (2) Pyrolyzing the leaching solution obtained in the step (1), and filtering to obtain lithium carbonate precipitation and pyrolyzed solution; (3) And (3) performing coprecipitation reaction on the pyrolyzed liquid obtained in the step (2) and a sodium hydroxide solution to obtain a ternary precursor. Further, in the step (1), the concentration of the NTA solution is 1-10 mol/L, and more preferably 3-8 mol/L. Further, in the step (1), the concentration of the bicarbonate solution is 1 to 3mol/L, and more preferably 1 to 2 mol/L. Further, in the step (1), the volume ratio of the NTA solution to the bicarbonate solution is 1:1-5:1, and more preferably 2:1-5:1. In the step (1), the leaching solid-liquid ratio of the positive electrode powder is 10 to 100 g/L, and more preferably 20 to 50 g/L. Further, in the step (1), the temperature at the time of leaching is 30 to 90 ℃, and more preferably 50 to 80 ℃. Further, in the step (2), the pyrolysis temperature of the leaching solution is 50-100 ℃, and more preferably 60-90 ℃. Further, in the sodium hydroxide solution in the step (3), the mass fraction of sodium hydroxide is 10-30%, and more preferably 15-30%. Further, in the step (3), the pH of the reaction is controlled to be 10 to 12, more preferably 11 to 12, in the coprecipitation reaction process. Further, in the step (3), the coprecipitation reaction time is 5 to 20 hours, and more preferably 10 to 20 hours. The invention has the beneficial effects that: (1) The invention creatively adopts the metal complexing agent NTA to replace ammonia water which has pungent smell and is easy to volatilize, and the complexing sequence of the NTA in the solution is nickel, cobalt, manganese, iron and magnesium in turn, so that the nickel, cobalt and manganese are leached in the leaching process, impurity elements exist in leaching slag, an additional impurity removing process is not needed, the recover