Oxidative and reductive leaching methods

Patent metadata

Field	Value
Publication number	US-2025305089-A1
Application number	US-202318881503-A
Country	US
Kind code	A1
Filing date	Aug 1, 2023
Priority date	Aug 9, 2022
Publication date	Oct 2, 2025
Grant date	—

Abstract

Disclosed herein are methods for obtaining a composition including copper sulfide from a material, where the methods include: contacting the material with an acidic aqueous solution having a pH less than 6 in the presence of sulfur dioxide to form copper sulfide; where the material includes one or more copper compounds chosen from copper in a zero oxidation state, copper oxide, and copper hydroxide, and where the material includes an amount of zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode. Also disclosed are methods for recycling at least one battery material, and compositions including copper sulfide.

First claim

1 . A method for obtaining a composition comprising copper sulfide from a material, wherein the method comprises:
contacting the material with an acidic aqueous solution having a pH less than 6 in the presence of sulfur dioxide to form copper sulfide; wherein no oxidizing agent is added during the contacting step; wherein the material comprises one or more copper compounds selected from the group consisting of copper in a zero oxidation state, copper oxide, and copper hydroxide; and wherein the material comprises an amount of zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode.

2 . The method according to claim 1 , further comprising separating the composition comprising copper sulfide from the aqueous solution by a solid-liquid separation.

3 . The method according to claim 1 , further comprising purifying the composition comprising copper sulfide by a solid-solid separation.

4 . The method according to claim 2 , wherein the composition comprises from 0.1 weight percent to 100 weight percent of copper sulfide; by total weight of the composition.

5 . The method according to claim 1 , wherein the acidic aqueous solution comprises H 2 SO 4 .

6 . The method according to claim 1 , wherein the material is a lithium ion battery material selected from the group consisting of black mass, cathode active material, cathodes, cathode current collector foils, cathode active material precursors, graphite, anodes, anode current collector foils, and combinations thereof.

7 . The method according to claim 1 , wherein the material comprises:
from 0 weight percent to 10 weight percent lithium, from 0.1 weight percent to 60 weight percent nickel, from 0 weight percent to 20 weight percent cobalt, from 0.1 weight percent to 20 weight percent aluminum, from 0 weight percent to 20 weight percent iron, from 0 weight percent to 20 weight percent manganese, and from 0 weight percent to 20 weight percent zinc; wherein each weight percent is by total weight of the material; wherein an amount of at least one of the nickel, cobalt, aluminum, iron, manganese, and zinc is present as a zero oxidation state metal; and wherein the material has a molar ratio of copper to the amount of zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode ranging from 1:0.1 to 1:10.

8 . The method according to claim 1 , wherein the material, or a precursor thereof, is pyrolyzed prior to the contacting step.

9 . The method according to claim 1 , wherein contacting the material with an acidic aqueous solution having a pH less than 6 in the presence of sulfur dioxide causes a formation of hydrogen gas and hydrogen sulfide gas, and wherein after the formation of hydrogen gas and hydrogen sulfide gas, the method comprises adding an oxidizing agent selected from the group consisting of O 2 , N 2 O, a mixture of air with 0.1 to 5 vol % sulfur dioxide, a mixture of oxygen with 0.1 to 5 vol % sulfur dioxide, and combinations thereof.

10 . The method according to claim 1 , further comprising adding air after the contacting step.

11 . The method according to claim 1 , wherein the acidic aqueous solution has a concentration of acid ranging from 18 mol/L to 0.0001 mol/L.

12 . The method according to claim 1 , wherein sulfur dioxide is fed during the contacting step as a gas at a rate of 1 to 500 Nl/kg of the material.

13 . The method according to claim 1 , wherein, subsequent to the contacting step, the method further comprises adding an additional material comprising one or more selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, metal bicarbonate, and combinations thereof.

14 . A method for recycling at least one battery material selected from the group consisting of a lithium ion battery, lithium ion battery waste, lithium ion battery production scrap, lithium ion cell production scrap, lithium ion cathode active material, and combinations thereof, wherein the method comprises:
optionally, heat treating the at least one battery material at a temperature ranging from 350° C. to 900° C., mechanically comminuting the at least one battery material to obtain a comminuted material, optionally, sorting the comminuted material to obtain a fine fraction and a course fraction, and subjecting the comminuted material, optionally the fine fraction, the course fraction, or the fine fraction and the course fraction, to the method according to claim 1 .

15 . The method according to claim 1 , further comprising smelting the composition comprising copper sulfide.

16 . The method according to claim 1 , further comprising roasting the composition comprising copper sulfide.

17 . A composition comprising copper sulfide prepared according to claim 1 .

18 . The method according to claim 2 , wherein the solid-liquid separation is selected from the group consisting of filtration, sedimentation, centrifugation, and combinations thereof.

19 . The method according to claim 3 , wherein the solid-solid separation is selected from the group consisting of flotation, magnetic separation, gravity separation, dense media separation, and combinations thereof.

20 . The method according to claim 1 , wherein one or more metals in a zero oxidation state selected from the group consisting of Ni, Co, Mn, Fe, and combinations thereof, is added to the material prior to and/or during the contacting step.

21 . The method according to claim 9 , wherein no oxidizing agent is added until after the hydrogen gas formation.

22 . The method according to claim 10 , wherein no air is added until at least 1 minute, at least 10 minutes, at least 30 minutes, at least 1 hour, or at least 2 hours, after the beginning of the contacting step.

23 . The method according to claim 1 , wherein the acidic aqueous solution is not sparged with an oxidizing agent (e.g., air) prior to the contacting step.

24 . The method according to claim 1 , wherein no oxidizing agent other than sulfuric acid is added to the acidic aqueous solution prior to the contacting step.

25 . The method according to claim 1 , wherein, at the beginning of the contacting step, less than 50 mol % of oxidizing agent, other than sulfuric acid, is present in the acidic aqueous solution by total moles of the copper in a zero oxidation state and the zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode.

26 . The method according to claim 1 , wherein, at the beginning of the contacting step, less than 25 mol % of oxidizing agent, other than sulfuric acid, is present in the acidic aqueous solution by total moles of the copper in a zero oxidation state and the zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode.

27 . The method according to claim 1 , wherein, at the beginning of the contacting step, less than 10 mol % of oxidizing agent, other than sulfuric acid, is present in the acidic aqueous solution by total moles of the copper in a zero oxidation state and the zero oxidation state metals having a standard redox-potential less than zero volt versus a standard hydrogen electrode.

28 . The method according to claim 1 , wherein, at the beginning of the contacting step, less t

Assignees

• Basf Se

Inventors

• Rohde Wolfgang
• Gerlach Till
• Magin Andrea
• Born Nils-Olof Joachim
• Schierle-Arndt Kerstin

Classifications

• H01M10/54

  Reclaiming serviceable parts of waste accumulators · CPC title

• C22B15/0028

  Smelting or converting · CPC title

• C22B15/0013

  by roasting · CPC title

• C22B7/007

  by acid leaching · CPC title

• C22B1/24

  Binding; Briquetting {; Granulating} · CPC title