Battery recycling

Patent metadata

Field	Value
Publication number	US-2023411724-A1
Application number	US-202118250136-A
Country	US
Kind code	A1
Filing date	Oct 20, 2021
Priority date	Oct 21, 2020
Publication date	Dec 21, 2023
Grant date	—

Abstract

A method (2800) of selectively leaching one or more manganese-containing phases from a mixed-phase battery electrode material comprises treating (2802) the mixed-phase battery electrode material with a solution of an acid, the acid acting as both a leaching agent and a reducing agent, so as to form a manganese-containing leachate whilst leaving at least one phase of the battery electrode material unleached, wherein the acid has a pKa greater than or equal to −2. Either or both of the leachate and the remaining electrode material may then be regenerated (2806, 2808).

First claim

1 - 28 . (canceled)

29 . A method of selectively leaching one or more manganese-containing phases from a mixed-phase battery electrode material, the method comprising:
treating the mixed-phase battery electrode material with a solution of an acid, the acid acting as both a leaching agent and a reducing agent, so as to form a manganese-containing leachate whilst leaving at least one phase of the battery electrode material unleached, wherein the acid has a pKa greater than or equal to −2.

30 . The method of claim 29 , wherein the mixed-phase battery electrode material is a cathode material from a sodium— or lithium-ion battery having a blended cathode.

31 . The method of claim 29 , wherein the acid is at least one organic acid.

32 . The method of claim 29 , wherein the acid has a pKa in the range from 2 to 12.

33 . The method of claim 29 , wherein the acid is ascorbic acid and the acid solution is an ascorbic acid solution with a molarity in the range from 0.25M to 1.5M.

34 . The method of claim 29 , wherein the treating of the electrode material is arranged to leach out at least substantially only phases in which manganese makes up at least 20% of the transition metal content.

35 . The method of claim 29 , wherein the electrode material is or comprises a blended cathode strip of LMO and a layered oxide, and wherein the treating of the electrode material is arranged to selectively leach out the LMO whilst leaving the layered oxide at least substantially intact.

36 . The method of claim 29 , wherein the treating of the electrode material comprises exposing the electrode material to the acid for a period of less than ten minutes.

37 . The method of claim 29 , wherein the treating of the electrode material comprises exposing the electrode material to the acid for a longer time period when treating electrode material from an end-of-life (used) battery than when treating electrode material from a quality-control rejected new battery.

38 . The method of claim 29 , wherein the treating of the electrode material is performed at a temperature of between 20° C. and 90° C.

39 . The method of claim 29 , wherein the electrode material comprises at least one unshredded cathode strip.

40 . The method of claim 35 , wherein the method further comprises re-generating an LMO phase from the leachate, the re-generating comprising:
drying the leachate so as to form a precipitate; grinding the precipitate; and annealing the ground precipitate in air or another oxygen-containing atmosphere.

41 . The method of claim 29 , wherein the electrode material comprises LMO or NaMO which is leached by the acid solution, and the method further comprises generating a target XNi x Mn y Co z O 2 (XNMC) phase from the leachate, where X is at least one of Li, Na, from the leachate, the generating comprising:
gravimetrically determining the amount of leached LMO or NaMO in the leachate, and, based on the gravimetrically determined amount of leached LMO or NaMO:
calculating a molar amount of a cobalt- and nickel-containing sulfate, M(SO 4 )—nH 2 O (where M=Co and Ni), required to obtain the target XNMC composition from the leachate; and
calculating a molar amount of a carbonate or hydroxide of X required to obtain the target XNMC composition from the leachate;
combining the calculated amount of M(SO 4 ) nH 2 O with the leachate; adding a molar amount of a soluble source of a cation selected to trigger the precipitation of a sulfate, so as to remove the sulfate from the leachate solution, the molar amount to add being calculated from the molar amount of M(SO 4 ) nH 2 O and the Co:Ni ratio of M to the leachate solution; drying the leachate solution so as to form a precipitate; grinding the precipitate with the calculated amount of a carbonate or hydroxide of X; and annealing the ground material in air or another oxygen-containing atmosphere.

42 . The method of claim 29 , wherein the electrode material comprises LMO or NaMO which is leached by the acid solution, and the method further comprises generating a target XNi x Mn y Co z O 2 (XNMC) phase from the leachate, where X is at least one of Li, Na, from the leachate, the generating comprising:
gravimetrically determining the amount of leached LMO or NaMO in the leachate, and, based on the gravimetrically determined amount of leached LMO or NaMO:
calculating a molar amount of a soluble source of cobalt and nickel required to obtain the target XNMC composition from the leachate; and
calculating a molar amount of a carbonate or hydroxide of X required to obtain the target XNMC composition from the leachate;
combining the calculated amount of the soluble source of cobalt and nickel with the leachate; adding an OH − source until a precipitate is formed; drying the precipitate; grinding the precipitate with the calculated amount of the carbonate or hydroxide of X; and annealing the ground material in air or another oxygen-containing atmosphere.

43 . The method of claim 42 , wherein the amount of the hydroxide added to form the precipitate is the amount of the hydroxide required to bring the solution pH to 11.

44 . The method of claim 29 , further comprising:
gravimetrically determining an amount of material lost from the mixed-phase battery electrode material into the leachate; and adding a stoichiometric amount of one or more reagents to the leachate to introduce desired metal cations, so as to generate a desired battery cathode material.

45 . A battery material regeneration method for resynthesizing a layered oxide with a composition of XNi x Mn y Co z O 2 (XNMC) or XNi x Co y Al z O 2 (XNCA) from a battery cathode, where X is Na, Li, or a mixture of the two, the method comprising:
obtaining an XNMC- or XNCA-containing electrode material from the battery cathode; combining the material with an OH − source, and heating the mixture to form a precipitate of NMC(OH) 2 or NCA(OH) 2 , as appropriate, with X going into solution; extracting and drying the NMC(OH) 2 or NCA(OH) 2 precipitate; grinding the precipitate with a gravimetrically-determined stoichiometric amount of a carbonate or hydroxide of X; and heating the resultant powder to resynthesize XNMC or XNCA.

46 . The method of claim 45 , wherein sodium hydroxide is used, and wherein the sodium hydroxide is provided as an aqueous NaOH solution with a molarity in the range from 0.5 M to 1 M.

47 . A lithium-ion and/or sodium-ion battery recycling method comprising:
obtaining battery electrode material, the battery electrode material comprising multiple phases at least one of which is manganese-containing; treating the battery electrode material with a solution of an acid with pKa greater than or equal to ˜2, the acid acting as both a leaching agent and a reducing agent so as to form a manganese-containing leachate whilst leaving at least one phase of the battery electrode material unleached, wherein the battery electrode material is exposed to the acid solution for a period of less than twenty minutes;
draining off the leachate; and
regenerating at least one unleached phase.

48 . The method of claim 47 , wherein the unleached phase is a layered oxide, and wherein the regenerating the unleached phase comprises:
forming a hydroxide of the unleached phase; grinding the hydroxide of the unleached phase with a stoichiometric amount of LiOH H 2 O for a Li-ion battery material, or NaOH H 2 O for a Na-ion battery material; and heating the resultant powder to resynthesise the

Assignees

• Univ Birmingham

Inventors

• Driscoll Laura Louise
• Slater Peter Raymond
• Anderson Paul Alexander

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

• C22B47/0063 Primary

  with acids or salt solutions (C22B47/0072 takes precedence) · CPC title

• C22B7/007

  by acid leaching · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title