Process for the recycling of spent lithium ion cells

Patent metadata

Field	Value
Publication number	US-2021324495-A1
Application number	US-201917250339-A
Country	US
Kind code	A1
Filing date	Jul 9, 2019
Priority date	Jul 10, 2018
Publication date	Oct 21, 2021
Grant date	—

Abstract

Process for the recovery of transition metal from spent lithium ion batteries containing nickel, wherein said process comprises the steps of (a) heating a lithium containing transition metal oxide material to a temperature in the range of from 200 to 900° C. in the presence of H 2 , (b) treatment of the product obtained in step (a) with an aqueous medium, (c) solid-solid separation for the removal of Ni from the solid residue of step (b), (d) recovery of Li as hydroxide or salt from the solution obtained in step (b), (e) extraction of Ni and, if applicable, Co from the solid Ni-concentrate obtained in step (c).

First claim

1 . A process for recovering transition metals from spent lithium ion batteries containing nickel (Ni), comprising the steps of:
(a) heating a lithium containing transition metal oxide material to a temperature ranging from 200° C. to 900° C. in the presence of H 2 , wherein the transition metal oxide material is from lithium ion batteries and contains fluorine compounds and/or compounds of phosphorous as impurities; (b) treating the material obtained in step (a) with an aqueous medium to form a solid residue and a solution; (c) removing by solid-solid separation Ni from the solid residue of step (b) forming a solid Ni-concentrate; (d) recovering lithium (Li) as a hydroxide or salt from the solution obtained in step (b); and (e) extracting Ni and/or cobalt (Co) from the solid Ni-concentrate obtained in step (c).

2 . A process for recovering transition metals from spent lithium ion batteries containing nickel (Ni), comprising the steps of:
(a) heating a lithium containing transition metal oxide material to a temperature ranging from 200° C. to 900° C. in the presence of hydrogen (H 2 ); (b) treating of the material obtained in step (a) with an aqueous medium to form a solid residue and a solution; (c) removing by solid-solid separation Ni from the solid residue of step (b); (d) recovering lithium (Li) as hydroxide or salt from the solution obtained in step (b) to form a solid Ni-concentrate; and (e) extracting Ni and/or cobalt (Co) from the solid Ni-concentrate obtained in step (c); wherein the lithium containing transition metal oxide material heated in step (a) is from lithium ion batteries and contains fluorine in an amount ranging from 2% to 8% by weight, and/or phosphorous in an amount ranging from 0.2% to 2% by weight, relative to the weight of the lithium containing transition metal oxide material.

3 . The process according to claim 1 , wherein the temperature in step (a) ranges from 350° C. to 500° C.

4 . The process according to claim 1 , wherein the lithium containing transition metal oxide material used in step (a) is from lithium ion batteries after mechanic removal of casing, wiring or circuitry and discharging, and wherein the material is not exposed to temperatures of 400° C. or more under oxidizing conditions before the heating of step (a).

5 . The process according to claim 1 , wherein the extracting of step (e) comprises smelting of the solid Ni-concentrate obtained in step (c).

6 . The process according to claim 1 , wherein the extracting of step (e) comprises treating the Ni-concentrate obtained in step (c) with a base.

7 . The process according to claim 5 , wherein the solution containing Ni and/or Co salt, are treated with ammonia or an alkali metal hydroxide to obtain a solution with a pH-value ranging from 2.5 to 8.

8 . The process according to claim 5 , wherein solution containing Ni and/or Co salts are treated with metallic nickel, metallic cobalt, or metallic manganese or any combination thereof.

9 . The process according to claim 1 , further comprising removing carbon or organic polymers by a dry solid-solid separation prior to step (b).

10 . The process according to claim 1 , wherein in step (d), lithium is recovered as lithium hydroxide.

11 . The process according to claim 1 , wherein in step (d), lithium is recovered by way of precipitation as carbonate.

12 . The process according to claim 1 , further comprising an additional step (f) of precipitating Ni and/or Co and/or manganese as (mixed) hydroxide, oxyhydroxide or carbonate.

13 . The process according to claim 1 , wherein step (a) is performed in the presence of steam.

14 . The process according to claim 1 , wherein step (a) is performed in the presence of lime, quartz, silica, silicate, or any combination thereof.

15 . The process according to claim 1 , further comprising an additional step before step (a) of contacting the material from spent lithium ion batteries with water and/or organic solvent followed by a solid-liquid separation step.

16 . The process according to claim 1 , wherein step (e) comprises treating the solid Ni-concentrate obtained in step (c) with an acid.

17 . The process according to claim 16 , wherein the acid is chosen from sulfuric acid, hydrochloric acid, nitric acid, methane sulfonic acid, oxalic acid, citric acid, and a combination thereof.

18 . The process according to claim 1 , wherein step (e) comprises treating the Ni-concentrate obtained in step (c) with ammonium bicarbonate or ammonium carbonate.

19 . The process according to claim 6 , wherein the base is chosen from ammonia; aqueous solutions of amines, ammonia, and/or ammonium carbonate; and a mixture of ammonia and carbon dioxide.

20 . The process according to claim 12 , wherein step precipitating in (f) comprises adding at least one agent chosen from lithium hydroxide, sodium hydroxide, ammonia, and potassium hydroxide.

21 . The process according to claim 12 , wherein precipitating in setp (f) is by raising a pH above 8.

22 . The process according to claim 3 , wherein 35% by volume or more of H 2 is present in step (a) and the temperature in step (a) ranges from 350° C. to 450° C.

Assignees

• Basf Se

Inventors

• Rohde Wolfgang
• Adermann Torben
• Schierle-Arndt Kerstin
• Gerke Birgit

Classifications

• Y02P10/20

  Recycling · CPC title

• Y02W30/84

  Recycling of batteries or fuel cells · CPC title

• C22B23/0415 Primary

  with acids or salt solutions except ammonium salts solutions · CPC title

• C22B7/007 Primary

  by acid leaching · CPC title

• C22B23/043

  Sulfurated acids or salts thereof · CPC title