Process for the recovery of lithium from waste lithium ion batteries

Patent metadata

Field	Value
Publication number	US-12410493-B2
Application number	US-202017597482-A
Country	US
Kind code	B2
Filing date	Jul 24, 2020
Priority date	Jul 26, 2019
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

A process for the recovery of lithium from waste lithium ion batteries or parts thereof is disclosed. The process comprising the steps of (a) providing a particulate material containing a transition metal compound and/or transition metal, wherein the transition metal is selected from the group consisting of Mn, Ni and Co, and wherein further at least a fraction of said Ni and/or Co, if present, are in an oxidation state lower than +2, and at least a fraction of said Mn, if present, is manganese(II)oxide; which particulate material further contains a lithium salt and a fluoride salt, and which particulate material optionally contains calcium provided that the element ratio calcium to fluorine is 1.7 or less or is zero; (b) treating the material provided in step (a) with a polar solvent and an alkaline earth hydroxide; and (c) separating the solids from the liquid, optionally followed by washing the solid residue with a polar solvent such as water provides good separation of lithium in high purity, and recovery of valuable transition metals.

First claim

The invention claimed is:

1. A process for recovering lithium from a particulate material comprising waste lithium ion batteries or parts thereof, wherein the process comprises:
(a) providing the particulate material comprising a transition metal compound and/or transition metal, wherein the transition metal is chosen from Mn, Ni, and Co, and wherein further at least a fraction of the Ni and/or Co, if present, are in an oxidation state lower than +2, and at least a fraction of the Mn, if present, is manganese(II)oxide; wherein the particulate material further comprises a lithium salt and a fluoride salt, and wherein the particulate material has a molar ratio of calcium to fluorine of 1.7 or less or zero,
(b) treating the particulate material in step (a) with a polar solvent and an alkaline earth hydroxide;
(c) separating solids from liquid of the particulate material in step (b), and optionally, washing the solid residue with a polar solvent, and
further comprising recovering lithium from the solid residue and/or the liquid of the particulate material in step (b).

2. The process of claim 1 , wherein the particulate material of step (a) is from waste lithium ion batteries and is in a form of a dry powder, wet powder, or suspension of particles in a liquid.

3. The process according to claim 1 , wherein the particulate material of step (a) comprises particles having an average particle diameter D50 ranging from 1 μm to 2 mm, when detected in accordance with ISO 13320 EN: 2009-10.

4. The process according to claim 1 , wherein the transition metal compound and/or transition metal Ni and/or Co in oxidation state lower than +2, comprised in the particulate material provided in step (a), comprises Ni and/or Co in the metallic state, and wherein the transition metal compound and/or transition metal comprised in the particulate material provided in step (a) is present in an amount detectable by powder x-ray diffractometry (Cu-k-alpha-1 radiation).

5. The process according to claim 1 , wherein the lithium salt and the fluoride salt of the particulate material of step (a) comprises one of more salts of LiOH, LiF, Li2O, Li2CO3, LiHCO3, lithium aluminates, lithium phosphate salts, and mixed oxides of Li and one or more of Ni, Co, Mn, Fe, Al, Cu and/or fluorides of Ni, Co, Mn, Fe, Al, Cu.

6. The process according to claim 1 , wherein treating in step (b) comprises:
i) adding the alkaline earth hydroxide and/or an alkaline oxide, as a solid, or a mixture comprising the alkaline earth hydroxide as suspension or solution in protic solvent, and the particulate material of step (a) simultaneously to the polar solvent, which is a protic solvent;
ii) adding the particulate material of step (a) to the polar solvent, which is a protic solvent, to obtain a suspension, followed by adding the alkaline earth hydroxide and/or an alkaline oxide, as a solid, or a mixture comprising alkaline earth hydroxide as suspension or solution in a protic solvent;
iii) adding the alkaline earth hydroxide and/or an alkaline oxide, as a solid or suspension of solids in a polar solvent, to an aqueous liquid to obtain a mixture comprising alkaline earth hydroxide, and subsequently combining the mixture with the particulate material of step (a);
iv) adding the alkaline earth hydroxide and/or an alkaline oxide, as a solid, to the particulate material of step (a) to obtain a mixture of solids, followed by adding the polar solvent;
or
v) adding the particulate material of step (a) to the polar solvent, which is a protic solvent, to obtain a suspension, followed by filtrating to obtain a filtrate, and subsequently adding the alkaline earth hydroxide and/or an alkaline oxide, as a solid, or a mixture comprising alkaline earth hydroxide to the filtrate.

7. The process according to claim 1 , wherein the alkaline earth hydroxide added in step (b) is calcium hydroxide added, or calcium hydroxide is formed in situ upon contact of calcium oxide with the polar solvent, which is a protic solvent.

8. The process according to claim 1 , wherein the particulate material of step (a) comprises material obtained from waste lithium ion batteries after carrying out a preliminary step (i) of heating under inert or reducing conditions to a temperature ranging from 80° C. to 900° C., wherein the preliminary step (i) is carried out after discharging the lithium ion batteries, dismantling, and/or shredding.

9. The process according to claim 8 , wherein the preliminary step (i) is conducted under reducing conditions comprising carbon and/or a reducing gas chosen from hydrogen and carbon monoxide.

10. The process according to claim 8 , wherein in the preliminary step (i) the temperature ranges from 350° C. to 500° C.

11. The process according to claim 1 , wherein the particulate material of step (a) is obtained from lithium ion batteries after mechanic removal of casing, wiring or circuitry and discharging, and wherein the particulate material is not exposed to temperatures of 400° C. or more under oxidizing conditions before step (a).

12. The process according to claim 1 , further comprising (d) subjecting the solids obtained in step (c) to a solid-solid separation.

13. The process according to claim 1 , further comprising (f) recovering the transition metals nickel and/or cobalt by pyrometallurgical or hydro-metallurgical treatment of the solid residue obtained after carrying out step (c).

14. The process according to claim 12 , further comprising (f) recovering the transition metals nickel and/or cobalt by pyrometallurgical or hydro-metallurgical treatment of the solid residue obtained after carrying out step (d).

15. The process according to claim 1 , further comprising
recovering lithium as lithium hydroxyde by crystallization from the liquid obtained in step (c), or recovering lithium as lithium carbonate after adding carbon dioxide to the liquid obtained in step (c) and isolating the lithium carbonate formed.

Assignees

• Basf Se

Inventors

• Rohde Wolfgang
• Gerke Birgit
• Schierle-Arndt Kerstin
• Adermann Torben
• Voges Matthias
• Vogelsang Regina

Classifications

• H01M10/54

  Reclaiming serviceable parts of waste accumulators · CPC title

• C22B26/12 Primary

  Obtaining lithium · CPC title

• C22B7/008 Primary

  by an alkaline or ammoniacal leaching · CPC title

• C01P2006/80

  Compositional purity · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title