Process for the recovery of lithium and other metals from waste lithium ion batteries

Patent metadata

Field	Value
Publication number	US-2022251681-A1
Application number	US-202017625753-A
Country	US
Kind code	A1
Filing date	Jul 24, 2020
Priority date	Jul 26, 2019
Publication date	Aug 11, 2022
Grant date	—

Abstract

A process for the recovery of one or more transition metals and 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 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, e.g. in the metallic state; which particulate material further contains a lithium salt; (b) treating the material provided in step (a) with a polar solvent and optionally an alkaline earth hydroxide; (c) separating the solids from the liquid, optionally followed by a solid-solid separation step; and (d) treating the solids containing the transition metal in a way to dissolve at least part of the Ni and/or Co, typically using a mineral acid, provides good separation of lithium in high purity and of transition metal useful for the production of battery cathode active materials.

First claim

1 - 16 . (canceled)

17 . A process for recovering one or more transition metals, and lithium as Li-salt from a particulate material comprising waste lithium ion batteries or parts thereof, wherein the process comprises:
(a) providing the particulate material comprises a transition metal compound and/or transition metal, wherein the transition metal is chosen from Ni and Co, and at least a fraction of the Ni and/or Co are in an oxidation state lower than +2 and wherein the particulate material further comprises a lithium salt; (b) treating the particulate material of step (a) with an alkaline earth hydroxide and a polar solvent; (c) separating solid residue comprising the transition metal from liquid of the particulate material of step (b), and optionally, subjecting the solid residue to a solid-solid separation for the removal of the transition metal; and (d) treating the solid residue of step (c) comprising the transition metal to dissolve at least part of the Ni and/or Co.

18 . The process according to claim 17 , wherein the particulate material of step (a) is from spent lithium ion batteries and/or scrap material from producing lithium ion batteries or lithium ion cathode active materials, and is in a form of a dry powder, wet powder, or suspension of particles in a liquid.

19 . The process according to claim 17 , 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.

20 . The process according to claim 17 , wherein the transition metal compound and/or transition metal Ni and/or Co in oxidation state lower than +2, comprised in the particulate material of 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 of step (a) is present in an amount detectable by powder x-ray diffractometry (Cu-k-alpha-1 radiation).

21 . The process according to claim 17 , wherein the lithium salt comprised in the particulate material of step (a) comprises one or 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.

22 . The process according to claim 17 , wherein treating in step (b) is carried out in presence of an alkaline earth hydroxide and 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 a 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 such as water 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, which is a protic 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.

23 . The process according to claim 17 , wherein the polar solvent of step (b) comprises calcium hydroxide, which is added to the polar solvent, or is formed in situ upon contact of calcium oxide with the polar solvent chosen from protic solvents.

24 . The process according to claim 17 , 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.

25 . The process according to claim 17 , wherein treating the solid residue of step (d) comprises treating with a mineral acid chosen from sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, oxalic acid and citric acid, or a combination of at least two of the foregoing.

26 . The process according to claim 24 , wherein in the preliminary step (i) the temperature ranges from 350° C. to 500° C., and the preliminary step (i) is conducted in the presence of 35% or more by volume of hydrogen; or
wherein in the preliminary step (i) the temperature ranges from 500° C. to 850° C., and the preliminary step (i) is conducted in the presence of carbon in an atmosphere containing up to 20% by volume of oxygen.

27 . The process according to claim 17 , 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).

28 . The process according to claim 17 , further comprising subjecting the solids of step (c) to a solid-solid separation.

29 . The process according to claim 17 , wherein the solids treated in step (d) further comprise one or more of copper, iron, and manganese.

30 . The process according to claim 17 , 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.

31 . The process according to claim 17 , wherein the transition metal obtained in step (d) is subjected to precipitation as hydroxide, and optionally, after removing undesired impurity metals and/or adding missing amounts of metals as corresponding salts, and optionally, followed by calcination to achieve a metal composition of a desired cathode active material.

32 . A cathode active precursor material produced by the process according to claim 17 .

Assignees

• Basf Se

Inventors

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

Classifications

• C22B3/12

  in inorganic alkaline solutions · CPC title

• C22B26/12 Primary

  Obtaining lithium · CPC title

• C22B15/0065

  Leaching or slurrying (with organic compounds C22B3/16) · CPC title

• C22B23/00 Primary

  Obtaining nickel or cobalt · CPC title

• C22B23/0407

  Leaching processes · CPC title