PROCESS FOR THE PURIFICATION OF LITHIUM SALTS

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 crude lithium hydroxide as a solid, which contains fluoride; and (B) dissolving the crude lithium hydroxide solid with a lower alcohol such as methanol or ethanol provides good separation of lithium in high purity.

Claims

1-12. (canceled)

13. An electrode active material comprising (A) a core material according to general formula Li.sub.1+x1TM.sub.1−x1O.sub.2, wherein TM is a combination of Ni and at least one of Mn, Co and Al, and, optionally, at least one more metal selected from Mg, Ti, Zr, Nb, Ta, and W, and x.sub.1 is in a range from −0.05 to 0.2, and (B) particles of cobalt compound(s), of aluminum compound(s), and of titanium compound(s) or of zirconium compound(s), wherein a molar ratio of lithium to cobalt in the particles is in a range of from zero to below 1, and wherein in the particles, a molar ratio of Co to the sum of Al and Zr or Ti is in a range from 2:1 to 50:1, and wherein the particles are attached to the surface of the core material.

14. The electrode active material according to claim 13, wherein TM is a combination of metals according to general formula (I)
(Ni.sub.aCo.sub.bMn.sub.c).sub.1−dM.sub.d  (I) with a in a range of from 0.6 to 0.95, b in a range of from 0.025 to 0.2, c in a range of from 0.025 to 0.2, and d in a range of from zero to 0.1, M is selected from Al, Mg, Ti, Zr, Nb, Ta, W, and combinations of at least two of the foregoing and
a+b+c=1.

15. The electrode active material according to claim 13, wherein an average oxidation state of cobalt is higher than +II and lower than +III.

16. The electrode active material according to claim 13, wherein the particles comprise Co.sub.3O.sub.4.

17. The electrode active material according to claim 13, wherein a weight ratio of core (A) and particles (B) ranges from 1000:1 to 1 to 1.

18. The electrode active material according to claim 13, wherein the particles (B) have an average diameter (D50) ranging from 10 nm to 10 μm.

19. A process for making an electrode active material comprising: (a) providing a material according to general formula Li.sub.1+x2TM.sub.1−x2O.sub.2, wherein TM is a combination of Ni and at least one of Mn, Co and Al, and, optionally, at least one more metal selected from Mg, Ti, Zr, Nb, Ta, and W, and x.sub.2 is in a range from zero to 0.25, (b) contacting the material with an oxide or (oxy)hydroxide of cobalt and, at least one oxide or hydroxide or oxyhydroxide of each of Al and Ti or Zr, and (c) calcining the intermediate of step (b).

20. The process according to claim 19, wherein step (c) is performed at a temperature ranging from 500° C. to 850° C.

21. The process according to claim 19, wherein step (b) is performed in a mixer.

22. The process according to any of claim 19, wherein step (b) is performed by adding an aqueous slurry of an oxide or (oxy)hydroxide of cobalt and, of at least one oxide or hydroxide or oxyhydroxide of each of Al and Ti or Zr to the material provided in step (a), followed by mixing.

23. An electrode containing (A) at least one electrode active material according to any of claim 13, (B) carbon in electrically conductive form and (C) a binder.

24. A secondary battery containing (1) at least one electrode according to claim 23, (2) at least one anode, and (3) an electrolyte.

Description

BRIEF DESCRIPTION OF FIGURES

[0190] FIG. 1: X-ray powder diffractogram (Mo Ka) of reduced mass from waste lithium ion batteries after heat/reduction treatment as obtained in example 1a and used in example 2a including reference diffractograms of graphite, cobalt, manganese-II-oxide, cobalt oxide, and nickel.

[0191] FIG. 2: X-ray powder diffractogram (Mo Ka) of reduced mass from waste lithium ion batteries after heat/reduction treatment as obtained in example 1a and used in example 2a including reference diffractograms of graphite, lithium aluminate, and lithium carbonate.

[0192] FIG. 3: X-ray powder diffractogram (Cu Ka) of reduced mass from waste lithium ion batteries after heat/reduction treatment as obtained in example 1a and used in example 2a including reference diffractograms of graphite, cobalt, manganese-II-oxide, cobalt oxide, and nickel.

[0193] FIG. 4: X-ray powder diffractogram (Cu Ka) of reduced mass from waste lithium ion batteries after heat/reduction treatment as obtained in example 1a and used in example 2a including reference diffractograms of graphite, lithium aluminate, and lithium carbonate.

[0194] The project leading to this application has received funding from Bundesministerium für Wirtschaft and Energie (DE; FKZ:16BZF101A); the applicant bears responsibility for all disclosures herein.