Recovery of critical elements from end-of-life lithium ion batteries with supported membrane solvent extraction

Patent metadata

Field	Value
Publication number	US-2021376400-A1
Application number	US-202016884189-A
Country	US
Kind code	A1
Filing date	May 27, 2020
Priority date	May 27, 2020
Publication date	Dec 2, 2021
Grant date	—

Abstract

Single-stage and multi-stage systems and methods for the recovery of critical elements in substantially pure form from lithium ion batteries are provided. The systems and methods include supported membrane solvent extraction using an immobilized organic phase within the pores of permeable hollow fibers. The permeable hollow fibers are contacted by a feed solution on one side, and a strip solution on another side, to provide the simultaneous extraction and stripping of elements from dissolved lithium ion cathode materials, while rejecting other elements from the feed solution. The single- and multi-stage systems and methods can selectively recover cobalt, manganese, nickel, lithium, aluminum and other elements from spent battery cathodes and are not limited by equilibrium constraints as compared to traditional solvent extraction processes.

First claim

1 . A method for the recovery of cobalt from lithium ion batteries, the method comprising:
dissolving a battery material containing Co and Li within an acid to form a feed solution, the feed solution including Co(II) and Li(I); providing a membrane module including a plurality of hollow fibers, the plurality of hollow fibers including a porous sidewall defining a lumen side spaced apart from a shell side; wetting the porous sidewall of the plurality of hollow fibers with an organic phase, the organic phase including a cationic extractant and an organic solvent; performing membrane solvent extraction by moving the feed solution along one of the lumen side or the shell side of the plurality of hollow fibers and simultaneously moving a strip solution along the other of the lumen side or the shell side of the plurality of hollow fibers, the strip solution including a pH that is less than a pH of the aqueous feed solution; maintaining a pH of the feed solution within a predetermined range by intermittently introducing a buffer or a base to the feed solution during membrane solvent extraction; wherein wetting the porous sidewall of the plurality of hollow fibers with the organic phase is performed prior to moving the feed solution and moving the strip solution, and wherein the cationic extractant in the porous sidewall continuously extracts Co(II) from the aqueous feed solution for recovery by the strip solution while substantially rejecting Li(I).

2 . The method of claim 1 wherein the feed solution includes a positive pressure differential with respect to the strip solution of between 1 psi and 5 psi.

3 . The method of claim 1 wherein the feed solution and the strip solution are moving in continuous recirculation through the membrane module for at least thirty minutes.

4 . The method of claim 1 further including separating the battery material from a spent battery cathode, wherein separating the battery material from a spent battery cathode includes subjecting the spent battery cathode to a thermal treatment, acid dissolution, and vacuum filtration.

5 . The method of claim 1 wherein the organic phase contained within the porous sidewall of the plurality of hollow fibers is substantially free of tributyl phosphate.

6 . A multi-stage recovery system comprising:
a first feed reservoir including a first feed solution containing dissolved battery material including a concentration of Li, Ni, Co, and Mn; a first membrane module including a first plurality of hollow fibers each having a porous sidewall that is pre-wetted with a first organic phase, the first membrane module receiving the first feed solution in continuous recirculation therethrough; a first strip reservoir in fluid communication with the first membrane module and including a first strip solution having Co and Mn extracted from the first feed solution; a second feed reservoir including a second feed solution containing a concentration of Co and Mn recovered from the first strip reservoir; a second membrane module including a second plurality of hollow fibers each having a porous sidewall that is pre-wetted with a second organic phase, the second membrane module receiving the second feed solution in continuous recirculation therethrough; and a second strip reservoir in fluid communication with the second membrane module and including a second strip solution having Co and Mn extracted from the second feed solution; wherein the first membrane module selectively recovers Co and Mn from the first feed solution while rejecting Li and Ni and wherein the second membrane module selectively recovers Co from the second feed solution while rejecting Mn.

7 . The system of claim 6 further including a third feed reservoir including a third feed solution containing a concentration of Li and Ni recovered from the first feed reservoir;
a third membrane module including a third plurality of hollow fibers each having a porous sidewall that is pre-wetted with a third organic phase, the third membrane module receiving the third feed solution in continuous recirculation therethrough; and
a third strip reservoir in fluid communication with the third membrane module and including a third strip solution having Ni extracted from the second feed solution;
wherein the third membrane module selectively recovers Ni from the first feed solution while rejecting Li.

8 . The system of claim 6 wherein the pH of the first feed solution is between 4 and 6, inclusive, and wherein the first organic phase includes a cationic extractant and an organic solvent.

9 . The system of claim 6 wherein the pH of the second feed solution is less than or equal to 1.5, and wherein the second organic phase includes a cationic extractant and an organic solvent.

10 . The system of claim 7 wherein the pH of the third feed solution is between 6 and 7.5, and wherein the third organic phase includes a cationic extractant and an organic solvent.

11 . A method for recycling battery material, the method comprising:
dissolving battery material containing Co, Mn, Li, and Ni within an acid to form a first feed solution and regulating the pH of the first feed solution between 4 and 6, inclusive; providing a first membrane module including a first plurality of hollow fibers, the first plurality of hollow fibers each including a lumen side and a shell side; wetting the first plurality of hollow fibers with a first organic phase, the first organic phase including a first cationic extractant; and after wetting the first plurality of hollow fibers, moving the aqueous feed solution along one of the lumen side or the shell side of the plurality of hollow fibers and simultaneously moving a strip solution along the other of the lumen side or the shell side of the plurality of hollow fibers; wherein the first cationic extractant continuously removes Co and Mn from the aqueous feed solution as a first-stage membrane solvent extraction while substantially rejecting Li and Ni, and wherein the strip solution continuously back extracts Co and Mn from the first organic phase.

12 . The method of claim 11 wherein regulating the pH of the first feed solution includes intermittently adding a buffer or a base to maintain the pH between 4 and 6, inclusive.

13 . The method of claim 11 wherein the first feed solution includes a positive pressure differential with respect to the first strip solution of between 1 psi and 5 psi.

14 . The method of claim 11 wherein moving the first feed solution and moving the first strip solution includes continuously recirculating the first feed solution and the first strip solution through the first membrane module for at least one hour.

15 . The method of claim 11 further including performing a second-stage membrane solvent extraction of the first strip solution, as a second feed solution, to recover Co while substantially rejecting Mn, and regulating the pH of the second feed solution to be less than or equal to 1.5.

16 . The method of claim 15 wherein the second-stage membrane solvent extraction includes:
providing a second membrane module including a second plurality of hollow fibers, the second plurality of hollow fibers including a lumen side and a shell side;
wetting the second plurality of hollow fibers with a second organic phase, the second organic phase including a second cationic extractant; and
moving the second feed solution along one of the lumen side or the shell side of the second plurality of hollow fibers and simultaneously moving a second strip solution along the other of the lumen side or the shell side of the second plurality of hol

Assignees

• Ut Battelle Llc

Inventors

• Bhave Ramesh R
• Islam Syed Z
• Wagh Priyesh A

Classifications

• C22B23/00

  Obtaining nickel or cobalt · CPC title

• B01D2311/18

  pH control · CPC title

• B01D11/0492

  Applications, solvents used · CPC title

• B01D11/0488

  Flow sheets · CPC title

• B01D11/0415

  in combination with membranes · CPC title