METHOD FOR THE HYDROMETALLURGICAL RECOVERY OF LITHIUM FROM THE LITHIUM MANGANESE OXIDE-CONTAINING FRACTION OF USED GALVANIC CELLS

• US 20150267278A1
• Filed: 10/09/2013
• Published: 09/24/2015
• Est. Priority Date: 10/10/2012
• Status: Active Grant

• Current Assignee: Albemarle Germany GmbH (Albemarle Corporation)
• Original Assignee: Rockwood Lithium Gmbh (Albemarle Corporation)
• Inventors: Wohlgemuth, David, Spielau, Rebecca, Willems, Johannes, Steinbild, Martin, Kliehm, Norbert, Scheider, Mark Andre
• Granted Patent: US 10,711,326 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C01B 25/45 containing plural metal, or metal and ammonium
• CPC Class Codes: C01D 15/02 Oxides; Hydroxides
• CPC Class Codes: C22B 26/12 Obtaining lithium
• CPC Class Codes: C22B 7/007 by acid leaching
• CPC Class Codes: H01M 10/54 Reclaiming serviceable parts of waste accumulators
• CPC Class Codes: Y02P 10/20 Recycling
• CPC Class Codes: Y02W 30/84 Recycling of batteries or fuel cells

Abstract

The invention relates to a method for the hydrometallurgical recovery of lithium from the lithium manganese oxide-containing fraction of used galvanic cells.

Claims

1-9. -9. (canceled)

10. A method for hydrometallurgical recovery of lithium from the fraction of used galvanic cells containing lithium manganese oxide, comprising the steps of:

adding the fraction containing lithium manganese oxide with a particle size up to 500 μ

m to oxalic acid in a hyper-stoichiometric amount relative to the manganese content in the lithium manganese oxide and is solubilized in a solid/liquid ratio in the range of 10 to 250 g/l at temperatures from 30 to 70°

C.;

separating lithium-containing solution formed; and

washing remaining residue is washed at least twice;

wherein the separated lithium and lithium-containing washing solution are combined, the dissolved manganese residue content is reduced by precipitation as hydroxide, separated and washed and the remaining lithium-containing solution is further purified by conversion into the carbonate, chloride or sulfate and preferably subsequent crystallization.

11. The method according to claim 10, wherein the content of multivalent metal cations is reduced by means of an ion exchanger.

12. The method according to claim 10, wherein the fraction containing lithium manganese oxide has a particle size up to 500 μ

m.

13. The method according to claim 11, wherein the fraction containing lithium manganese oxide has a particle size up to 500 μ

m.

14. The method according to claim 10, wherein the oxalic acid is used at a concentration of 0.2 to 1.2 mol/l.

15. The method according to claim 11, wherein the oxalic acid is used at a concentration of 0.2 to 1.2 mol/l.

16. The method according to claim 12, wherein the oxalic acid is used at a concentration of 0.2 to 1.2 mol/l.

17. The method according to claim 10, wherein the solid to liquid ratio is adjusted in the range of 20 to 200 g/l.

18. The method according to claim 10, wherein the solubilization is carried out at temperatures of 35 to 65°

C.

19. The method according to claim 10, wherein solubilization residue is washed at least three times.

20. The method according to claim 10, wherein the molar excess is from 0.1 to 1, preferably a molar excess of 0.2 to 0.8 is used.

21. The method according to claim 10, wherein a molar excess is from 0.2 to 0.8.

22. A method comprising preparing a lithium transition metal oxide or a lithium transition metal phosphate from the product prepared by the method of claim 10, and preparing a cathode for a lithium-ion battery comprising the lithium transition metal oxide or the lithium transition metal phosphate.