# US 12,119,464 B2 · Method for preferentially recovering manganese from waste lithium-rich manganese-based cathode material

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- Number: US 12,119,464 B2
- Document ID: US12119464B2
- Status: Granted
- Kind: B2
- Application number: 18/507,242
- Filed: 2023-11-13
- Published: 2024-05-23
- Granted: 2024-10-15
- Earliest claimed: 2022-11-21
- Assignees: Beijing University of Technology
- Applicants: Beijing University of Technology
- Inventors: Dean Pan; Xiaoguang Zhang; Yifan Wang; Qijun Zhang; Wei Wang
- Web page: https://patentgrep.com/patent/US12119464B2

## CPC

- H01M 10/54: Reclaiming serviceable parts of waste accumulators
- C22B 1/005: {Preliminary treatment of scrap (C22B1/02 - C22B1/26 take precedence)}
- C22B 1/06: Sulfating roasting
- 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 3/26: by liquid-liquid extraction using organic compounds
- C22B 3/38: containing phosphorus
- C22B 7/00: Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; {Methods of a general interest or applied to the winning of more than two metals (briquetting of scrap C22B1/248; preliminary treatment of scrap C22B1/005)}
- C22B 7/006: {Wet processes}
- C22B 7/007: {by acid leaching}
- C22B 47/00: Obtaining manganese
- 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

The present invention provides a method for preferentially recovering manganese from waste lithium-rich manganese-based cathode material, the method comprising: step 1) calcination and leaching: mixing the waste lithium-rich manganese-based cathode material with ammonium sulfate and then performing low-temperature calcination, leaching the calcination product with water, and then performing solid-solution separation to obtain a leaching solution; step 2) complexing and manganese separating: adding ammonium sulfite to the leaching solution obtained in step 1) for a complex reaction to obtain manganese-rich residue; step 3) oxidation leaching: adding an oxidant to the manganese-rich residue obtained in step 2) to perform oxidation leaching, and adjusting the pH of the solution to obtain a manganese-rich solution; and step 4) extracting and stripping. The method realizes the preferential and productive recovering of manganese from waste lithium-rich manganese-based cathode materials, avoids the negative impact of polymetals in the conventional recovery process, and has economic and environmental benefits.

## Claims

### Claim 1

A method for preferentially recovering manganese from a waste lithium-rich manganese-based cathode material, comprising:
step 1) calcining and leaching: mixing the waste lithium-rich manganese-based cathode material with ammonium sulfate and then performing low-temperature calcination to obtain a calcination product, leaching the calcination product with water, and performing solid-solution separation after the completion of the water leaching to obtain leaching residue and a leaching solution;
step 2) complexing and manganese separating: adding ammonium sulfite to the leaching solution obtained in step 1) for a complex reaction, aging after the completion of the complex reaction, and filtering after the completion of the aging to obtain manganese-rich residue and a manganese-separated solution; in step 2), the amount of ammonium sulfite added is 3-5 times @ theoretical value of manganese complex in the leaching solution; and in step 2), when the complex reaction is performed, the pH value of the complex solution is adjusted to 7-10 with ammonia water; the complex reaction temperature is 25-70° C.; the complex reaction time is 20-60 min; and the aging time is 1-8 h;
step 3) oxidation leaching: adding an oxidant to the manganese-rich residue obtained in step 2) to perform oxidation leaching, adding 98% concentrated sulfuric acid to adjust the pH of the solution, and obtaining a manganese-rich solution after the completion of the reaction; in step 3), when performing oxidation leaching, the oxidant is hydrogen peroxide; the amount of hydrogen peroxide added is 0.5-2 mol per liter of the solution; and the solid-solution ratio of the leaching is 1:5-1:20 g/mL; and in step 3), the pH of the solution is adjusted to 1-5 with 98% concentrated sulfuric acid; the leaching temperature is 25-60° C.; and the leaching time is 10-25 min; and
step 4) extracting and stripping: performing multi-stage extraction of manganese on the manganese-rich solution obtained in step 3) to obtain a manganese-loaded organic phase and a raffinate; mixing the raffinate with the manganese-separated solution obtained in step 2) for a recovery treatment, and stripping the manganese-loaded organic phase to obtain a manganese sulfate solution.

### Claim 2 (depends on 1)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 1, wherein:
in step 1), when performing low-temperature calcination, the amount of ammonium sulfate added is 1.1-1.5 times a theoretical reaction number of moles of Li, Ni, Mn, and Co combined in the waste lithium-rich manganese-based cathode material; the calcination temperature is 300-500° C.; and the calcination holding time is 15-35 min.

### Claim 3 (depends on 2)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 2, wherein:
in step 1), when the calcination product is leached with water, the solid-solution ratio of the leaching is 1:5-1:20 g/mL; the leaching temperature is 25-60° C.; and the leaching time is 20-40 min.

### Claim 4 (depends on 3)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 3, wherein:
in step 4), an extractant is one of P204 and P507; a saponification agent is ammonia water with a molar concentration of 5-15 mol/L; a diluent is sulfonated kerosene;
the extraction O/A phase ratio is 1:1-1:3; the extraction pH value is 1-5; the extraction temperature is 25-45° C.; the extraction time is 5-25 min; and the number of extraction stages is 2-5.

### Claim 5 (depends on 4)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 4, wherein:
in step 4), the manganese-loaded organic phase is stripped with 2-6 mol/L sulfuric acid; the stripping O/A phase ratio is 3:1-1:1; the stripping temperature is 25-45° C.; the stripping time is 10-30 min; and the number of stripping stages is 2-5, to obtain the manganese sulfate solution.

### Claim 6 (depends on 5)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 5, wherein:
in step 1), when performing low-temperature calcination, the amount of ammonium sulfate added is 1.5 times the theoretical reaction number of moles of Li, Ni, Mn, and Co combined in the waste lithium-rich manganese-based cathode material; the calcination temperature is 500° C.; and the calcination holding time is 35 min; when the calcination product is leached with water, the solid-solution ratio of the leaching is 1:20 g/mL; the leaching temperature is 60° C.; and the leaching time is 35 min;
in step 2), the amount of ammonium sulfite added is 5 times the theoretical value of manganese complex in the leaching solution; when the complex reaction is performed, the pH value of the complex solution is adjusted to 10 with ammonia water; the complex reaction temperature is 70° C.; the complex reaction time is 60 min; and the aging time is 8 h;
in step 3), when performing oxidation leaching, the oxidant is hydrogen peroxide; the amount of hydrogen peroxide added is 2 mol per liter of solution; and the solid-solution ratio of the leaching is 1:20 g/mL; the pH of the solution is adjusted to 5 with 98% concentrated sulfuric acid; the leaching temperature is 60° C.; and the leaching time is 25 min; and
in step 4), the extractant is P204; the saponification agent is ammonia water with a molar concentration of 15 mol/L; the diluent is sulfonated kerosene; the extraction O/A phase ratio is 1:3; the extraction pH value is 5; the extraction temperature is 45° C.; the extraction time is 25 min; and
the number of extraction stages is 5; the manganese-loaded organic phase is stripped with 6 mol/L sulfuric acid; the stripping O/A ratio is 3:1; the stripping temperature is 45° C.; the stripping time is 30 min; and the number of stripping stages is 5.

### Claim 7 (depends on 1)

The method for preferentially recovering manganese from the waste lithium-rich manganese-based cathode material of claim 1, wherein:
the amount of ammonium sulfate added is 1.1 to 1.5 times a theoretical molar amount required for a reaction with Li, Ni, Mn, and Co in the waste lithium-rich manganese-based cathode material.