Mixed sodium and lithium period four transition metal oxides for electrochemical lithium extraction

Patent metadata

Field	Value
Publication number	US-2023323552-A1
Application number	US-202218044137-A
Country	US
Kind code	A1
Filing date	Feb 1, 2022
Priority date	Feb 2, 2021
Publication date	Oct 12, 2023
Grant date	—

Abstract

Layered Period Four transition metal oxide materials composed of lithium transition metal oxides and sodium transition metal oxides, in which the transition metal oxide is cobalt, manganese, nickel, or a combination of two or more thereof or provided. Also provided are electrochemical cells incorporating the layered transition metal oxides as electrode materials and methods for extracting dissolved lithium from solution using the electrochemical cells. In the materials a lithium transition metal oxide phase and a sodium transition metal oxide phase exist as separate phases connected by a transition region of intermediate composition and layer spacing to form a stable structure.

First claim

1 . A layered Period Four transition metal oxide material comprising:
a Li 0.94 MO 2 phase, where M is Co, Mn, Ni, or a combination of two or more thereof; a Na x MO 2 phase, where 0.45≤x≤0.51 and M is Co, Mn, Ni, or a combination of two or more thereof; and a transition region between the Li 0.94 MO 2 phase and the Na x MO 2 phase, the transition region comprising a Period Four transition metal oxide phase having a layer spacing that is intermediate between a layer spacing of the Li 0.94 MO 2 phase and a layer spacing of the Na x MO 2 phase.

2 . The layered Period Four transition metal oxide material of claim 1 , having a core-shell structure in which the Li 0.94 MO 2 phase is contained in a lithium-rich core and the Na x MO 2 phase is contained in a sodium-rich shell at least partially surrounding the lithium-rich core.

3 . The layered Period Four transition metal oxide material of claim 1 , having a core-shell structure in which the Na x MO 2 phase is contained in a sodium-rich core and the Li 0.94 MO 2 phase is contained in a lithium-rich shell at least partially surrounding the lithium-rich core.

4 . The layered Period Four transition metal oxide material of claim 1 , wherein the Li 0.94 MO 2 phase is a Li 0.94 CoO 2 phase, and the Na x MO 2 phase is an Na x CoO 2 phase.

5 . A method of forming a layered Period Four transition metal oxide material comprising:
a Li 0.94 MO 2 phase, where M is Co, Mn, Ni, or a combination of two or more thereof; a Na x MO 2 phase, where 0.45≤x≤0.51 and M is Co, Mn, Ni, or a combination of two or more thereof; and a transition region between the Li 0.94 MO 2 phase and the Na x MO 2 phase, the transition region comprising a Period Four transition metal oxide phase having a layer spacing that is intermediate between a layer spacing of the Li 0.94 MO 2 phase and a layer spacing of the Na x MO 2 phase, the method comprising: electrochemically delithiating LiMO 2 , where M is Co, Mn, Ni, or a combination of two or more thereof, in an electrolyte solution to form a partially delithiated lithium Period Four transition metal oxide; and conducting a non-Faradaic cation-exchange on the partially delithiated lithium Period Four transition metal oxide in a solution containing dissolved sodium ions to form the layered Period Four transition metal oxide material.

6 . The method of claim 5 , wherein the partially delithiated lithium Period Four transition metal oxide is a partially delithiated lithium cobalt oxide.

7 . A method of forming a layered Period Four transition metal oxide material comprising:
a Li 0.94 MO 2 phase, where M is Co, Mn, Ni, or a combination of two or more thereof; a Na x MO 2 phase, where 0.45≤x≤0.51 and M is Co, Mn, Ni, or a combination of two or more thereof; and a transition region between the Li 0.94 MO 2 phase and the Na x MO 2 phase, the transition region comprising a Period Four transition metal oxide phase having a layer spacing that is intermediate between a layer spacing of the Li 0.94 MO 2 phase and a layer spacing of the Na x MO 2 phase, the method comprising: conducting a non-Faradaic cation-exchange on Na y MO 2 , where M is Co, Mn, Ni, or a combination thereof and 0.5≤y<1, in a solution containing dissolved lithium ions to form the layered Period Four transition metal oxide material.

8 . The method of claim 7 , wherein the Na y MO 2 is Na 0.67 CoO 2 .

9 . An electrochemical cell for the extraction of lithium ions from a solution comprising lithium ions, the electrochemical cell comprising:
a cell compartment; a lithium storage electrode in the cell compartment, the lithium storage electrode comprising a layered Period Four transition metal oxide material comprising:
a Li 0.94 MO 2 phase, where M is Co, Mn, Ni, or a combination of two or more thereof;
a Na x MO 2 phase, where 0.45≤x≤0.51 and M is Co, Mn, Ni, or a combination of two or more thereof; and
a transition region between the Li 0.94 MO 2 phase and the Na x MO 2 phase, the transition region comprising a Period Four transition metal oxide phase having a layer spacing that is intermediate between a layer spacing of the Li 0.94 MO 2 phase and a layer spacing of the Na x MO 2 phase; and
a counter electrode in the cell compartment, wherein the counter electrode is in electrical communication with the lithium storage electrode.

10 . The electrochemical cell of claim 9 , wherein the counter electrode comprises a sodiated material.

11 . The electrochemical cell of claim 10 , wherein the sodiated material comprises NaFePO 4 .

12 . A method of extracting lithium from an electrolyte solution containing dissolved lithium ions using an electrochemical cell comprising:
a cell compartment; a lithium storage electrode in the cell compartment, the lithium storage electrode comprising a layered Period Four transition metal oxide material comprising:
a Li 0.94 MO 2 phase, where M is Co, Mn, Ni, or a combination of two or more thereof;
a Na x MO 2 phase, where 0.45≤x≤0.51 and M is Co, Mn, Ni, or a combination of two or more thereof; and
a transition region between the Li 0.94 MO 2 phase and the Na x MO 2 phase, the transition region comprising a Period Four transition metal oxide phase having a layer spacing that is intermediate between a layer spacing of the Li 0.94 MO 2 phase and a layer spacing of the Na x MO 2 phase; and
a counter electrode in the cell compartment, wherein the counter electrode is in electrical communication with the lithium storage electrode, the method comprising: introducing an electrolyte solution comprising dissolved lithium ions into the cell compartment; and applying a bias voltage across the lithium storage electrode and the counter electrode, wherein the application of the bias voltage drives the intercalation of lithium ions from the electrolyte solution into the layered Period Four transition metal oxide material.

13 . The method of claim 12 , further comprising:
replacing the electrolyte solution with a lithium recovery solution; replacing the counter electrode with a second counter electrode; and applying a reverse bias voltage across the lithium storage electrode and the second counter electrode, wherein the application of the reverse bias voltage drives the deintercalation of lithium ions from the layered Period Four transition metal oxide material into the lithium recovery solution to recover the lithium.

14 . The method of claim 13 , wherein the electrolyte solution further comprises dissolved sodium ions, and the lithium ions are recovered with a selectivity of at least 1×10 4 .

15 . The method of claim 13 , wherein the electrolyte solution further comprises dissolved sodium ions, and the lithium ions are recovered with a selectivity of at least 1×10 5 .

16 . The method of claim 13 , further comprising removing the lithium ions from the lithium recovery solution.

17 . The method of claim 13 , wherein the electrolyte solution comprises seawater

Assignees

• Univ Chicago

Inventors

• Liu Chong
• Hill Grant T

Classifications

• C25C7/02 Primary

  Electrodes (consumable anodes for the refining the metals C25C1/00 - C25C5/00); Connections thereof · CPC title

• C25C1/02

  of light metals · CPC title

• H01M4/131 Primary

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/505

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