CN-117305597-B - Leaching method of valuable metal of waste anode material

Abstract

The invention belongs to the field of waste battery recovery, and in particular relates to a leaching method of valuable metals of waste positive electrode materials, which comprises the steps of placing waste positive electrode materials containing M metal elements in a leaching solution containing a component A and a component B for leaching treatment, then separating oil from water to obtain a water phase A and an oil phase, carrying out back extraction treatment on the oil phase to obtain a regenerated phase enriched with the component A and a back extraction liquid, merging the water phase A and the back extraction liquid to obtain a leaching solution enriched with the metal M metal elements, wherein the component A is shown as a formula 1 Wherein the component B is inorganic sodium salt. The process has excellent leaching effect and also has excellent circulating leaching effect.

Inventors

• ZHANG WENCHAO
• LONG QING
• LI YANYU
• LIN ZHANG
• HUANG RUI
• CHAI LIYUAN
• GUO LIN
• DENG HAOYU
• OuYang Xinyue
• Deng Puqu

Assignees

• 中南大学

Dates

Publication Date

20260505

Application Date

20230919

Claims (16)

1. 1. A leaching method of valuable metals of waste positive electrode materials is characterized in that waste positive electrode materials containing M metal elements are placed in leaching solution containing component A and component B for leaching treatment, then water phase A and oil phase are obtained through oil-water separation, and the oil phase is subjected to back extraction treatment to obtain regenerated phase enriched with the component A and back extraction liquid; the component A is a solution of formula 1; 1 (1) The component B is at least one of sodium chloride and sodium nitrate; in the leaching solution, the weight ratio of the component A to the component B is 1-1.5:1; The M comprises Li and at least one of Ni, co and Mn; in the leaching stage, regulating the pH value in the leaching process to 7-10 by alkali liquor; the temperature of the leaching stage is 50-100 ℃; the leaching time is 2.5-20 h.
2. 2. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the waste positive electrode materials are materials stripped from positive electrode plates of waste lithium ion batteries, and the active materials in the waste positive electrode materials are lithium oxide salts of at least one metal of nickel, cobalt and manganese.
3. 3. The method for leaching valuable metals from waste positive electrode materials according to claim 2, wherein the waste positive electrode materials further comprise at least one of a conductive agent, a binder, an electrolyte and a diaphragm.
4. 4. The method for leaching valuable metals from waste positive electrode materials according to claim 2, wherein the content of the metal M in the waste positive electrode materials is more than 20 wt.%.
5. 5. The method for leaching valuable metals from waste positive electrode materials according to claim 4, wherein the content of the metal M in the waste positive electrode materials is 30-50wt%.
6. 6. The method for leaching valuable metals from waste anode materials according to claim 1, wherein the waste anode materials are subjected to grinding and sieving in advance; grinding for 30 min-60 min; The screened screen is a 100-mesh screen.
7. 7. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the component A is obtained by reacting a compound of formula a and a compound of formula b; a, a Formula b; The A - is an anion of at least one of Cl - 、NO 3 - 、Ac - ; and B + is at least one cation of Li + 、Na + 、K + .
8. 8. The method for leaching valuable metals from waste positive electrode materials according to claim 7, wherein the molar ratio of the formula a to the formula b is 1:0.95-1.05; The solvent in the reaction stage is an aqueous solvent; The temperature of the reaction stage is 50-90 ℃; The reaction time is 3-4 h.
9. 9. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the weight ratio of the component A to the component B in the leaching solution is 1.3-1.4:1.
10. 10. The method for leaching valuable metals from waste anode materials according to claim 1, wherein the pH value in the leaching process is regulated to 8.5-9.5 by alkali liquor in the leaching stage.
11. 11. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the alkaline solution is an aqueous solution of alkali metal hydroxide.
12. 12. The method for leaching valuable metals from waste anode materials according to claim 1, wherein the leaching time is 3-12 hours.
13. 13. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the stripping agent in the stripping process is an acid solution.
14. 14. The method for leaching valuable metals from waste positive electrode materials according to claim 13, wherein the stripping agent in the stripping process is an aqueous solution of inorganic acid.
15. 15. The method for leaching valuable metals from waste positive electrode materials according to claim 13, wherein the concentration of the solute of the acid solution is 0.5-5 m.
16. 16. The method for leaching valuable metals from waste positive electrode materials according to claim 1, wherein the regenerated phase is used as component a and recycled to the leaching process.

Description

Leaching method of valuable metal of waste anode material Technical Field The invention relates to the field of battery material recovery, in particular to the field of waste anode material recovery. Background Lithium ion batteries have become one of the sources of nickel-containing hazardous waste due to their limited cycle life and high nickel content. Along with the mass exploitation of metal minerals, the enrichment of valuable metals from the ternary positive electrode material of the waste lithium battery is a necessary trend for realizing the harmless and recycling of the waste lithium battery. At present, the method for extracting valuable metals from the ternary cathode material of the waste lithium battery mainly comprises pyrometallurgy, hydrometallurgy, bioleaching and the like. For example, china patent publication No. CN116154346A discloses a method for regenerating a waste lithium battery positive electrode material, which comprises the following steps of S1, adding acid into the waste lithium battery positive electrode material, carrying out selective lithium extraction reaction at 160-240 ℃, separating to obtain filtrate and filter residue 1, wherein the filter residue 1 is a nickel cobalt manganese compound, and the filtrate is a lithium salt solution, S2, mixing a lithium source 1, a transition metal source and an additive solution to obtain a mixed solution 1, then mixing the mixed solution with the filter residue 1 obtained in S1, carrying out hydrothermal reaction, separating a reaction product to obtain filter residue 2 and filtrate, and S3, carrying out ball milling on the filter residue 2 obtained in S2 and the lithium source 2, and calcining the obtained mixed material to obtain the lithium battery regenerated positive electrode material. For another example, chinese patent publication No. CN116102080a discloses a method of carbon thermal reduction treatment of waste cathode material and anode material, separating sodium from metal by water leaching, evaporating and crystallizing sodium in the leaching solution to obtain sodium carbonate, leaching the leached metal leaching residue by acid to separate high-purity nickel-manganese-iron solution and leaching residue, preparing a precursor by using the nickel-manganese-iron solution, mixing the precursor with sodium carbonate, and sintering in a muffle furnace to obtain NaNi 0.4Fe0.2Mn0.4O2 cathode material with excellent electrochemical properties. Most of the existing methods have the defects of high energy consumption, high pollution, long time consumption, limited leaching effect on low-content valuable metals, high leaching agent recycling difficulty, high three-waste treatment pressure and the like. Therefore, it is necessary to provide a method for extracting valuable metals from the ternary positive electrode material of the waste lithium battery in a high-efficiency and green manner. Disclosure of Invention Aiming at solving the problems of unsatisfactory metal recovery rate, large three-waste output and the like of the existing waste positive electrode material, the invention aims to provide a leaching method of valuable metals of the waste positive electrode material, and aims to provide an organic metal leaching method with a leaching agent capable of being recycled and having excellent leaching performance. A leaching method of valuable metals of waste positive electrode materials comprises the steps of placing waste positive electrode materials containing M metal elements into a leaching solution containing components A and B for leaching treatment, then performing oil-water separation to obtain a water phase A and an oil phase, and performing back extraction treatment on the oil phase to obtain a regenerated phase (regenerated leaching solvent) enriched with the component A and a back extraction solution; The component A is a solution (liquid formula 1) of the formula 1; the component B is inorganic sodium salt; in the leaching treatment stage, controlling the pH value of the system to be more than 3; the M comprises at least one of Ni, co, mn, li. Innovative research shows that the method adopts the component A and the component B to leach the waste anode material, and further cooperates with the joint control of the pH value of the leaching stage, so that the method can realize cooperation, and can obtain excellent leaching effect of the metal M without transforming the waste anode material, and more importantly, the leached component has excellent recycling capability. In the invention, the waste positive electrode material contains Li and at least one of Ni, co and Mn. For example, the active material can be a lithium oxide salt of at least one metal of nickel cobalt manganese. In the invention, the waste anode material also comprises at least one of a conductive agent, a binder, electrolyte and a diaphragm; In the invention, the content of the active material in the waste positive electrode material is not particu