Charge material for recycled lithium-ion batteries

Patent metadata

Field	Value
Publication number	US-11955613-B2
Application number	US-202117412742-A
Country	US
Kind code	B2
Filing date	Aug 26, 2021
Priority date	Apr 4, 2012
Publication date	Apr 9, 2024
Grant date	Apr 9, 2024

Abstract

Cathode material from exhausted lithium ion batteries are dissolved in a solution for extracting the useful elements Co (cobalt), Ni (nickel), Al (Aluminum) and Mn (manganese) to produce active cathode materials for new batteries. The solution includes compounds of desirable materials such as cobalt, nickel, aluminum and manganese dissolved as compounds from the exhausted cathode material of spent cells. Depending on a desired proportion, or ratio, of the desired materials, raw materials are added to the solution to achieve the desired ratio of the commingled compounds for the recycled cathode material for new cells. The desired materials precipitate out of solution without extensive heating or separation of the desired materials into individual compounds or elements. The resulting active cathode material has the predetermined ratio for use in new cells, and avoids high heat typically required to separate the useful elements because the desired materials remain commingled in solution.

First claim

What is claimed is:

1. In a recycling stream of exhausted secondary batteries, a method of recycling charge materials from the batteries for use in production of recycled batteries, comprising:
receiving a granular mass from a recycling stream based on dismantled batteries, the recycling stream including a plurality of charge materials defined by a battery chemistry of the dismantled batteries, each charge material of the plurality of charge materials defined by a metal and having an oxidation state, the battery chemistry defining a ratio of the charge materials for inclusion in a recycled battery;
adding a leach acid to the granular mass for reducing a pH of the leach solution to dissolve the charge materials in the leach solution, the leach acid selected based on an oxidation state of metal ions defining the dissolved charge materials in the leach solution;
performing a ratio adjustment of the charge materials for achieving a predetermined molar ratio of the charge materials in the leach solution; and
adding a base to the leach solution for raising the pH to precipitate a granular form of compounds of the charge materials, the granular form defining a charge material precursor responsive to sintering to form the recycled batteries.

2. The method of claim 1 wherein the ratio adjustment includes sampling a molar ratio of the charge materials in the leach solution, and if the molar ratio is different than the predetermined molar ratio for the recycled battery, adding additional charge materials for achieving the predetermined molar ratio of the charge materials dissolved in the leach solution.

3. The method of claim 2 wherein the additional charge materials are selected based on a compound corresponding to the leach acid.

4. The method of claim 1 wherein the oxidation state of each of the metal ions in the leach solution is equal to the others of the metal ions in the leach solution.

5. The method of claim 1 wherein the oxidation state of each of the metal ions defining the charge materials is 2+.

6. The method of claim 5 further comprising adding a reductant to the leach solution for achieving an oxidation state of 2+for the charge materials in the leach solution.

7. The method of claim 6 further comprising selecting the reductant based on a solubility constant (ksp) of the reductant in combination with the charge materials.

8. The method of claim 6 further comprising adding a reductant selected from the group consisting of hydrogen peroxide, hypophosphorous acid, sodium hypophosphite, phosphorous acid, hydrogen sulfide, sodium bisulfide, sodium sulfide, sodium bisulfite, sodium sulfite, sodium dithionite, sodium thiosulfate, hydrazine, carbon monoxide, nitric oxide and sulfur dioxide.

9. The method of claim 1 wherein the leach acid includes at least one of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, boric acid, hydrofluoric acid, hydrobromic acid, perchloric acid, and hydroiodic acid.

10. The method of claim 1 wherein the charge materials include Ni, Mn and Co and define the battery chemistry of the recycled battery.

11. The method of claim 1 further comprising selecting the leach acid and adjusting the pH based on a solubility constant (ksp) for forming a spherical particle of the precipitated charge materials.

12. The method of claim 1 wherein ratio adjustment further comprises adding a dopant, the dopant having a volume less than 1% of the charge material and selected based on a stability of a resulting crystalline structure of sintered charge material.

13. The method of claim 12 wherein at least a portion of the dopant is preexisting in the leach solution based on the recycling stream, and the ratio adjustment further comprises identifying a percentage of the dopant in the leach solution and adding additional dopant based on a percentage of the preexisting dopant.

14. The method of claim 1 further comprising:
following the addition of the leach acid, adjusting a pH of the leach solution for: precipitating impurities in the leach solution resulting from the recycling stream; and
leaving the charge materials in a solution form.

15. The method of claim 14 further comprising:
adjusting a pH of the leach solution to a range between 0-5;
inserting electrodes for electrodeposition into the leach solution; and
applying a voltage between 0.5 and 2.0v to the electrodes for electrodeposition of copper remaining in the leach solution.

16. The method of claim 14 further comprising, prior to the electrodeposition of copper, adjusting the pH to a range between 3.0 and 6.5 for precipitating impurities including Fe, Al and Cu.

17. The method of claim 14 further comprising, following addition of the leach acid, adjusting the pH to a range between 3.0 and 5.0 for precipitating Fe from the leach solution.

18. The method of claim 14 further comprising, following addition of the leach acid, adjusting the pH to a range between 5.0 and 7.0 for precipitating Cu from the leach solution.

Assignees

• Worcester Polytech Inst

Inventors

• Wang Yan
• Gratz Eric
• Sa Qina
• Zheng Zhangfeng
• Heelan Joseph
• Kim Kee-Chan

Classifications

• C01G53/82

  Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• H01M10/54 Primary

  Reclaiming serviceable parts of waste accumulators · CPC title

• C22B1/24

  Binding; Briquetting {; Granulating} · CPC title

• C22B7/007

  by acid leaching · CPC title

• C22B23/0423

  Halogenated acids or salts thereof · CPC title