Granted Patent B2

US 12,218,322 · App. 17/569,584 · Granted Feb 4, 2025

Inventors: Xunbing Liu (Yiyang, CN); Jianjun Ouyang (Yiyang, CN); Xijuan Liu (Yiyang, CN); Shanmu Wu (Yiyang, CN); Xiangping Zhao (Yiyang, CN); Xiongwu Dong (Yiyang, CN); Chaowen Zhang (Yiyang, CN); Quncheng Zhou (Yiyang, CN); Chun Luo (Yiyang, CN); Sanxian Chen (Yiyang, CN)

Assignee: HUNAN JIN YUAN NEW MATERIALS JOINT STOCK COMPANY LIMITED

H01M10/54C22B3/08C22B3/22C22B7/007C22B23/0461C22B26/12C22B47/00

Abstract

Claims (15)

1. A method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes, comprising the following steps:

a, disassembling waste ternary batteries to obtain waste ternary battery powder, and leaching the waste ternary battery powder with an acid for removing copper, iron and aluminum to obtain an impurity-removed solution;

b, adjusting a pH of the impurity-removed solution to 5.5-6.5 with sodium hydroxide, precipitating a mixture of cobalt hydroxide and nickel hydroxide, filtering and washing to obtain a filter cake and a filtrate, and treating the filter cake and the filtrate respectively;

c, dissolving the filter cake, which is a mixture of cobalt hydroxide and nickel hydroxide, with sulfuric acid, then, adjusting the pH to 5.0-6.0, adding fluoride into the dissolving solution to remove calcium and magnesium ions, filtering and washing to obtain a filtrate, allowing the filtrate to enter into a first impurity extraction procedure, removing impurities deeply, allowing raffinate to enter into a second extraction procedure, performing the second extraction procedure cobalt ion full extraction and full back-extraction to obtain a high-concentration pure solution of cobalt sulfate, evaporating and crystallizing the solution to obtain a battery-grade cobalt sulfate product, and allowing a nickel sulfate solution as the raffinate to enter into a third impurity extraction procedure;

d, obtaining pure nickel sulfate liquid as the raffinate after the third impurity extraction procedure, adjusting the pH to 6-10 with sodium hydroxide, precipitating nickel hydroxide, reversely washing the precipitates with pure water for 2-4 times to obtain a filter cake which is battery-grade nickel hydroxide, and treating the filtrate and the washing solution by a wastewater station for recycling;

e, adding sodium sulfide into the filtrate and the washing solution obtained in step b to remove the residual cobalt and nickel ions, filtering and washing to obtain a filter cake which is a mixture of cobalt sulfide and nickel sulfide, returning to the acid dissolution procedure, and allowing the filtrate and the washing solution to enter into the manganese precipitation procedure; and

in step e of adding sodium sulfide, solid sodium sulfide is added by 2.0-5.0 times of the total amount of cobalt and nickel in the filtrate and the washing solution obtained in step b; and the reaction lasts for 30-60 minutes to recover the residual cobalt and nickel ions;

f, adjusting the pH of the filtrate and the washing solution obtained in step e to 8-11 with sodium hydroxide, to precipitate manganese ions, filtering and washing to obtain a manganese hydroxide filter cake and a lithium-containing filtrate and washing solution;

g, evaporating and crystallizing sodium sulfate from the lithium-containing filtrate and washing solution to obtain a concentrated lithium solution, precipitating lithium carbonate with sodium carbonate, filtering and washing to obtain a lithium carbonate filter cake and a lithium precipitation mother liquor.

2. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes of claim 1 , wherein the sodium hydroxide is liquid alkali with a concentration of less than 32% or solid sodium hydroxide.

3. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes of claim 1 , wherein the pH of the impurity-removed solution is adjusted to 6-6.2 with sodium hydroxide.

4. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes according to claim 1 , wherein the concentration of the sulfuric acid is 5-80%.

5. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes according to claim 4 , wherein the concentration of the sulfuric acid is 30-78%.

6. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes of claim 1 , wherein in adding fluoride to remove calcium and magnesium ions, fluoride is added for 5-10 times of a total amount of calcium and magnesium ions in the dissolving solution; and the reaction lasts for 10-60 min to precipitate calcium and magnesium ions.

7. The method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes according to claim 6 , wherein the fluoride is one of sodium fluoride, ammonium fluoride and potassium fluoride.

Assignments (1)

Priority Claims (3)

Continuity (2)

References Cited (15)