Electrochemical lithium extraction for battery materials

Patent metadata

Field	Value
Publication number	US-2022411948-A1
Application number	US-202217843392-A
Country	US
Kind code	A1
Filing date	Jun 17, 2022
Priority date	Jun 23, 2021
Publication date	Dec 29, 2022
Grant date	—

Abstract

A method that includes contacting a Li-containing aqueous liquid with a Li ion-selective membrane while simultaneously applying an electric field thereby extracting Li ions from the Li-containing aqueous liquid; and intercalating the extracted Li ions into a cathode material.

First claim

What is claimed is:

1 . A method comprising:
contacting a Li-containing aqueous liquid with a Li ion-selective membrane while simultaneously applying an electric field thereby extracting Li ions from the Li-containing aqueous liquid; and intercalating the extracted Li ions into a cathode material.

2 . The method of claim 1 , wherein the cathode material comprises MO x , MF y , or MS z , where M=Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Si, Ge, Sn, Pb, P, As, Sb; 0≤x≤4; 0≤y≤6; and 0≤z≤4, and the Li-containing aqueous liquid is seawater, a brine, an underground source of concentrated salt water, a Li-recycle solution, or an industry waste.

3 . The method of claim 1 , wherein the cathode material comprises an electrolytic manganese dioxide.

4 . The method of claim 1 , further comprising passing the extracted Li ions through a nonaqueous liquid electrolyte prior to intercalating the extracted Li ions into the cathode material.

5 . The method of claim 3 , further comprising passing the extracted Li ions through a nonaqueous liquid electrolyte prior to intercalating the extracted Li ions into the electrolytic manganese dioxide.

6 . The method of claim 1 , wherein the applied electric field has a voltage of −2V to 3V vs. SHE.

7 . The method of claim 3 , wherein the Li-containing aqueous liquid is seawater, a brine, an underground source of concentrated salt water, a Li-recycle solution, or an industry waste.

8 . The method of claim 3 , wherein the Li-containing aqueous liquid is seawater.

9 . The method of claim 3 , wherein the Li-containing aqueous liquid is brine.

10 . The method of claim 3 , wherein the Li-containing aqueous liquid is geothermal brine.

11 . The method of claim 3 , wherein the Li-containing aqueous liquid is a Li-recycle solution.

12 . The method of claim 3 , wherein the Li-containing aqueous liquid is industry waste solution.

13 . The method of claim 1 , wherein the Li ion-selective membrane comprises LiAB(PO 4 ) 3 (A=Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La; B═Ge, Ti or Zr), perovskite-type lithium lanthanum titanate, LISICON structure, Li 5 La 3 M 2 O 12 (M=Ta, Nb), Li 6 ALa 2 M 2 O 12 (A=Ca, Sr, Ba), or Li 5 Ln 3 Sb 2 O 12 (Ln=La, Pr, Nd, Sm, or Eu).

14 . The method of claim 1 , wherein the Li ion-selective membrane comprises Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 .

15 . The method of claim 5 , wherein the nonaqueous liquid electrolyte comprises at least one active salt and at least one solvent

16 . The method of claim 15 , wherein the active salt is lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium bis(oxalato)borate (LiBOB), LiPF 6 , LiAsF 6 , LiBF 4 , LiCF 3 SO 3 , LiClO 4 , lithium difluoro oxalato borate (LiDFOB), LiI, LiBr, LiCl, LiSCN, LiNO 3 , LiNO 2 , or Li 2 SO 4 .

17 . The method of claim 15 , wherein the solvent is an alkyl carbonate, an ether, or an ester.

18 . The method of claim 3 , wherein the Li-intercalated electrolytic manganese dioxide has a Li content of from >0 to ≤2 mol Li per molar electrolytic manganese dioxide.

19 . The method of claim 3 , further comprising producing a battery cathode material from the Li-intercalated electrolytic manganese dioxide substrate.

20 . The method of claim 19 , wherein the battery cathode material comprises spinel LiMn 2 O 4 , LiMn x Ni y Co z O 2 (wherein x+y+z=1), LiMPO 4 (M=Mn, Fe, Ni, Co or their mixture), or Li 2 MSiO 4 (M=Mn, Fe, Ni, Co or their mixture).

21 . A method comprising:
introducing a Li-containing aqueous liquid into a first chamber of a device, wherein the device comprises an anode, a cathode comprising electrolytic manganese dioxide, a Li ion-selective membrane between the anode and the cathode, the first chamber contacting the anode a first surface of the Li ion-selective membrane; and a second chamber contacting the cathode and a second surface of the Li ion-selective membrane, wherein the second chamber contains a nonaqueous liquid electrolyte; applying an electric field to the device; permitting Li ions to selectively flow through the Li ion-selective membrane and into the second chamber; and intercalating the extracted Li ions into the electrolytic manganese dioxide.

22 . The method of claim 21 , wherein the Li-containing aqueous liquid is seawater, a brine, or a Li-recycle solution; the Li ion-selective membrane comprises Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; the nonaqueous liquid electrolyte comprises at least one active salt and at least one solvent, wherein the active salt is lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium bis(oxalato)borate (LiBOB), LiPF 6 , LiAsF 6 , LiBF 4 , LiCF 3 SO 3 , LiClO 4 , lithium difluoro oxalato borate (LiDFOB), LiI, LiBr, LiCl, LiSCN, LiNO 3 , LiNO 2 , or Li 2 SO 4 ; and the solvent is an alkyl carbonate, an ether, or an ester.

23 . A device comprising:
an anode; a cathode comprising electrolytic manganese dioxide; a Li ion-selective membrane between the anode and the cathode; a first chamber contacting the anode a first surface of the Li ion-selective membrane; and a second chamber contacting the cathode and a second surface of the Li ion-selective membrane.

24 . The device of claim 23 , wherein the anode comprises stainless steel, nickel, titanium, tungsten, carbon, or graphite.

25 . The device of claim 23 , wherein the Li ion-selective membrane comprises LiAB(PO 4 ) 3 (A=Al, Cr, Ga, Fe, Sc, In, Lu, Y, or La; B═Ge, Ti or Zr), perovskite-type lithium lanthanum titanate, LISICON structure, Li 5 La 3 M 2 O 12 (M=Ta, Nb), Li 6 ALa 2 M 2 O 12 (A=Ca, Sr, Ba), or Li 5 Ln 3 Sb 2 O 12 (Ln=La, Pr, Nd, Sm, or Eu).

Assignees

• Battelle Memorial Institute

Inventors

• Lu Dongping
• Asmussen Robert M
• Kuo Li-Jung
• Hu Jiangtao

Classifications

• C25C1/02 Primary

  of light metals · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C22B3/42

  by ion-exchange extraction · CPC title

• C22B26/12

  Obtaining lithium · CPC title

• H01M4/0459

  Electrochemical doping, intercalation, occlusion or alloying · CPC title