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CN-121992203-A - Method for precipitating and recovering valuable metal from waste lithium ion battery

CN121992203ACN 121992203 ACN121992203 ACN 121992203ACN-121992203-A

Abstract

The invention belongs to the field of waste lithium ion battery material recovery, and particularly relates to a method for recovering valuable metals from waste lithium ion batteries by precipitation. The recovery method comprises the steps of vulcanizing and roasting the black powder of the waste battery, eluting lithium with water to preferentially recover valuable metal lithium, adding the leached slag after lithium extraction into acid leaching solution after impurity removal to carry out leaching treatment of the valuable metal, enabling the valuable metal in the black powder to enter the acid leaching solution in an ionic form, carrying out a series of impurity removal treatments such as selective precipitation and step extraction on the acid leaching solution to obtain a purified solution containing nickel cobalt manganese metal, and respectively precipitating nickel cobalt manganese in the purified solution to realize the recovery and reutilization of Li, ni, co, mn. The recycling process is green and pollution-free, and the used raw and auxiliary materials are high in safety. Compared with the traditional extraction and back extraction process using an extractant, the metal recovery process has the advantages of environmental protection and low cost, and the reaction process is safe and controllable, so that the method has good industrial application prospect.

Inventors

  • WANG XINCHANG
  • CUI CAIXIA
  • JIA QIANLIN

Assignees

  • 郑州大学

Dates

Publication Date
20260508
Application Date
20260303
Priority Date
20251204

Claims (10)

  1. 1. A method for precipitation recovery of valuable metals from waste lithium ion batteries, said valuable metals comprising one or more of lithium, nickel, cobalt and manganese, comprising the steps of: Discharging, disassembling and separating the waste lithium ion batteries to obtain anode and cathode black powder; mixing the anode and cathode black powder with sulfuric acid for vulcanization roasting, eluting lithium from the obtained roasted black powder by water, and carrying out solid-liquid separation to obtain a lithium-containing leaching solution and lithium-washing leaching residues; mixing the lithium-containing leaching solution with carbonate for reaction, and carrying out solid-liquid separation to obtain lithium carbonate; Performing alkaline leaching impurity removal on the lithium leaching residues by adopting alkaline liquor, and performing solid-liquid separation to obtain alkaline leaching impurity removal filter residues; leaching the alkaline leaching impurity-removed filter residues by adopting acid liquor to obtain a leaching solution containing nickel, cobalt and manganese; Regulating the pH value of the pickle liquor containing nickel, cobalt and manganese to 3.5-5, performing a first precipitation reaction, and performing solid-liquid separation to obtain a first impurity-removing filtrate; Mixing the first impurity removal filtrate with fluoride salt to perform a second precipitation reaction, and performing solid-liquid separation to obtain a second impurity removal filtrate; Mixing the second impurity removing filtrate with a copper extractant to perform first extraction impurity removal to obtain a third impurity removing filtrate; Mixing the third impurity removal filtrate with a phosphate extractant to perform second extraction impurity removal to obtain a purified solution containing nickel, cobalt and manganese; Mixing the purified solution containing nickel, cobalt and manganese with dimethylglyoxime to obtain nickel-containing precipitate, mixing the purified solution containing nickel, cobalt and manganese or the filtrate after nickel precipitation with oxalic acid to obtain cobalt-containing precipitate, and mixing the purified solution containing nickel, cobalt and manganese or the filtrate after nickel precipitation or the filtrate after cobalt precipitation with carbonate to obtain manganese-containing precipitate.
  2. 2. The method according to claim 1, wherein the temperature of the vulcanization roasting is 400-600 ℃, the heat preservation time is 1-4 hours, and the temperature of the water-leached lithium is 70-90 ℃.
  3. 3. The method according to claim 1 or 2, wherein the temperature of the mixing reaction of the lithium-containing leaching solution and the carbonate is 70-90 ℃ and the time is 0.5-1.5 h.
  4. 4. The method according to claim 1, wherein the alkali solution is sodium hydroxide solution or potassium hydroxide solution, the concentration of the alkali solution is 0.5-3 mol/L, the temperature of the alkali leaching impurity removal is 50-70 ℃ and the time is 0.5-2 h.
  5. 5. The method according to claim 1 or 4, wherein the acid solution is obtained by mixing sulfuric acid and hydrogen peroxide solution, the concentration of H 2 SO 4 in the acid solution is 1-6 mol/L, the mass concentration of the hydrogen peroxide solution is 30%, the volume ratio of the hydrogen peroxide solution in the acid solution is 10-30vol%, the leaching temperature is 30-80 ℃ and the leaching time is 0.5-2H.
  6. 6. The method of claim 1, wherein the first precipitation reaction is performed at a temperature of 30-60 ℃ for a time of 1-2 hours.
  7. 7. The method according to claim 1, wherein the fluoride salt is sodium fluoride, the sodium fluoride is used in the form of a sodium fluoride solution, the concentration of the sodium fluoride solution is 0.2-1.5 mol/L, the volume ratio of the sodium fluoride solution to the first impurity removal filtrate is 0.1-0.3:1, the temperature of the second precipitation reaction is 40-80 ℃, and the time is 0.5-2 h.
  8. 8. The method according to claim 1, wherein the copper extractant is M5640, the temperature of the first extraction impurity removal is 10-30 ℃, and the reaction time is 5-30 min.
  9. 9. The method according to claim 1, wherein the phosphate extractant is di (2-ethylhexyl) phosphate, the second extraction impurity removal temperature is 10-30 ℃, and the reaction time is 5-30 min.
  10. 10. The method of claim 1, wherein the molar ratio of the dimethylglyoxime to nickel ions in the nickel-cobalt-manganese-containing purified solution is 2-2.1:1, the nickel is precipitated after the pH value of the nickel-cobalt-manganese-containing purified solution is adjusted to 6-6.5, and the temperature of the mixing reaction of the nickel-cobalt-manganese-containing purified solution and the dimethylglyoxime is 60-90 ℃ for 10-60 min; the molar ratio of the oxalic acid to cobalt ions in the purified solution containing nickel cobalt and manganese is 1.5-2.5:1, the pH value of the purified solution containing nickel cobalt and manganese or the filtrate after nickel precipitation is adjusted to 2-2.5, and cobalt precipitation is carried out, wherein the temperature of the mixed reaction of the purified solution containing nickel cobalt and manganese or the filtrate after nickel precipitation and oxalic acid is 45-60 ℃ and the time is 30-90 min; The carbonate is sodium carbonate, and the sodium carbonate is used in the form of saturated sodium carbonate solution; the molar ratio of the carbonate to manganese ions in the purified solution containing nickel cobalt and manganese is 2-3:1, the pH value of the purified solution containing nickel cobalt and manganese or the filtrate after nickel precipitation or the filtrate after cobalt precipitation is adjusted to 7-7.5, manganese precipitation is carried out, the temperature of the mixed reaction of the purified solution containing nickel cobalt and manganese or the filtrate after nickel precipitation or the filtrate after cobalt precipitation and the carbonate is 25-50 ℃, and the time is 45-90 min.

Description

Method for precipitating and recovering valuable metal from waste lithium ion battery The present application claims priority from the chinese patent office filed 12 months 04 2025, application number CN202511820935.9, chinese patent application entitled "a method for recovering valuable metals from waste lithium ion batteries by precipitation", the entire contents of which are incorporated herein by reference. Technical Field The invention belongs to the field of waste lithium ion battery material recovery, and particularly relates to a method for recovering valuable metals from waste lithium ion batteries by precipitation. Background As a new type of clean electrochemical energy storage device, lithium ion batteries are increasingly used in a wide range, and are small in size for 3C products such as mobile phones, computers, video cameras, etc., and large in size in the fields of automobiles, communications, aerospace, etc. The lithium ion battery is used as movable energy storage equipment, so that the lithium ion battery is convenient for people to use, and meanwhile, the problem of disposal after the service life is finished is also solved. After the waste batteries cannot be used completely, the batteries are disassembled, recovered and extracted to obtain valuable metals, and the valuable metals are used as raw materials for preparing new batteries. After the scrapped waste batteries are collected uniformly, discharging treatment is firstly carried out, then crushing and disassembling are carried out, and the battery shell, the diaphragm, the anode powder, the cathode powder and the like are separated in a classified mode. The positive electrode powder contains a large amount of valuable metals such as nickel cobalt manganese lithium and the like, and can be recycled. The main methods for recovering valuable metals of the waste batteries include wet recovery, pyrogenic recovery, bioleaching and the like. The fire recovery process involves high temperature, consumes large energy, and can produce a large amount of waste slag to cause environmental pollution. The bioleaching process is green and pollution-free, but the strain culture period is too long, the requirement on growth conditions is high, and the process period is too long, so that the economic benefit is not good. The wet recovery has been widely studied and developed because of its advantages of high recovery efficiency, low energy consumption, high product purity, and the like. However, in the traditional wet recovery process, acid-base leaching is carried out on the waste battery black powder, then impurity removal treatment is carried out, then a pure solution containing valuable metals is obtained, then each metal ion in the solution is separated and extracted by using a corresponding extractant according to the characteristics of each solution, and then back extraction is carried out, so that a large amount of extractants are consumed in the process, and the raw material cost is high. Disclosure of Invention In view of the above, the invention aims to provide a method for precipitating and recovering valuable metals from waste lithium ion batteries. The invention can separate out various metal ions by adjusting the pH value of the solution and adding the precipitant after removing impurities from the leaching solution, and has the advantages of low cost and no pollution of the used raw materials, and compared with the extraction agent, the invention has the advantages of reduced raw material cost, simple process flow and no need of back extraction flow. The invention provides a method for precipitating and recovering valuable metals from waste lithium ion batteries, wherein the valuable metals comprise one or more of lithium, nickel, cobalt and manganese, and the method comprises the following steps of: Discharging, disassembling and separating the waste lithium ion batteries to obtain anode and cathode black powder; mixing the anode and cathode black powder with sulfuric acid for vulcanization roasting, eluting lithium from the obtained roasted black powder by water, and carrying out solid-liquid separation to obtain a lithium-containing leaching solution and lithium-washing leaching residues; mixing the lithium-containing leaching solution with carbonate for reaction, and carrying out solid-liquid separation to obtain lithium carbonate; Performing alkaline leaching impurity removal on the lithium leaching residues by adopting alkaline liquor, and performing solid-liquid separation to obtain alkaline leaching impurity removal filter residues; leaching the alkaline leaching impurity-removed filter residues by adopting acid liquor to obtain a leaching solution containing nickel, cobalt and manganese; Regulating the pH value of the pickle liquor containing nickel, cobalt and manganese to 3.5-5, performing a first precipitation reaction, and performing solid-liquid separation to obtain a first impurity-removing filtrate; Mixing the first i