# US 12,218,322 B2 · Manganese-lithium separation process and pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes

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- Number: US 12,218,322 B2
- Document ID: US12218322B2
- Status: Granted
- Kind: B2
- Application number: 17/569,584
- Filed: 2022-01-06
- Published: 2022-05-26
- Granted: 2025-02-04
- Earliest claimed: 2019-09-14
- Assignees: Hunan Jin Yuan New Materials Joint Stock Company Limited
- Applicants: Hunan Jin Yuan New Materials Joint Stock Company Limited
- Inventors: Xunbing Liu; Jianjun Ouyang; Xijuan Liu; Shanmu Wu; Xiangping Zhao; Xiongwu Dong; Chaowen Zhang; Quncheng Zhou; Chun Luo; Sanxian Chen
- Web page: https://patentgrep.com/patent/US12218322B2

## CPC

- H01M 10/54: Reclaiming serviceable parts of waste accumulators
- C22B 3/08: Sulfuric acid {, other sulfurated acids or salts thereof}
- C22B 3/22: by physical processes, e.g. by filtration, by magnetic means {, or by thermal decomposition} (treatment or purification of solutions by liquid-liquid extraction C22B3/26)
- C22B 3/3842: {Phosphinic acid, e.g. H2P(O)(OH)}
- C22B 3/3846: {Phosphoric acid, e.g. (O)P(OH)3}
- C22B 7/005: {Separation by a physical processing technique only, e.g. by mechanical breaking}
- C22B 7/007: {by acid leaching}
- C22B 23/0415: {with acids or salt solutions except ammonium salts solutions}
- C22B 23/043: {Sulfurated acids or salts thereof}
- C22B 23/0461: {by chemical methods}
- C22B 23/0476: {Separation of nickel from cobalt}
- C22B 26/12: Obtaining lithium
- C22B 47/00: Obtaining manganese
- C22B 47/0063: {with acids or salt solutions (C22B47/0072 takes precedence)}
- Y02P 10/20: Recycling
- Y02W 30/84: Recycling of batteries or fuel cells
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C22B: PRODUCTION AND REFINING OF METALS (electrolytic C25); PRETREATMENT OF RAW MATERIALS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

A manganese-lithium separation process and a pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and a method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from the ternary battery wastes, relates to a method for recycling battery wastes. According to the present disclosure, cobalt and nickel ions are separated from an impurity-removed solution by a hydrolysis method; manganese, lithium and other ions in the impurity-removed solution are free from an extraction procedure, so that most manganese ions are separated and removed by a wet method before extraction, to prevent the manganese ions from entering the extraction system; nickel ions are free from an extraction procedure of full extraction and full back-extraction; and nickel hydroxide is directly precipitated after related impurities are removed by extraction.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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%.

### Claim 5 (depends on 4)

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%.

### Claim 6 (depends on 1)

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.

### Claim 7 (depends on 6)

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.