Thin film metal and metal oxide anodes for rechargeable batteries

Patent metadata

Field	Value
Publication number	US-2024290965-A1
Application number	US-202418437163-A
Country	US
Kind code	A1
Filing date	Feb 8, 2024
Priority date	Feb 23, 2023
Publication date	Aug 29, 2024
Grant date	—

Abstract

A discharged electrochemical cell as described herein comprises an electrochemically reactive metal-containing cathode (e.g., Li, Na, Mg, or Zn; preferably Li) and a layered anode with an electrolyte therebetween. The layered anode comprises a conductive substrate and a reactive film of a metal, a semimetal, a metal oxide, or a semimetal oxide on the surface of the substrate. The reactive film is capable of reversibly alloying with, reversibly forming a mixed phase with, or reversibly reacting with, metal from cathode during charging of cell, and releasing the metal back to the cathode during discharge of the cell.

First claim

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1 . A rechargeable electrochemical cell comprising, in a fully discharged state: a cathode and a layered anode with an electrolyte therebetween; wherein the cathode comprises an electrochemically reactive first metal selected from the group consisting of Li, Na, Mg, and Zn; the layered anode comprises an electrically conductive substrate and a reactive film on a surface of the substrate in contact with the electrolyte; the reactive film comprises (a) an elemental metal or a semimetal selected from the group consisting of B, Mg, Al, Ca, Zn, Ga, Ge, As, Sr, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, Ir, Pt, Au, Hg, TI, Pb, and Bi, or (b) an oxide of a metal or a semimetal selected from the group consisting of Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Y, Zr, Nb, Mo, In, Sn, Sb, Te, La, Ce, Hf, Ta, W, Pb, and Bi; and the electrolyte comprises ions of the reactive metal of the cathode; wherein the reactive film alloys with, forms a mixed phase with, or reacts with, the first metal from the cathode during charging of the cell, and releases the first metal back to the cathode during discharging of the cell to reconstitute the reactive film; and the reactive film has a thickness of about 1 to 100 nm.

2 . The electrochemical cell of claim 1 , wherein the cathode comprises lithium and the reactive film comprises at least one elemental metal selected from the group consisting of Mg, Al, Ga, Sn, In, Ag, Au, Pt, Zn, Pb, and Bi.

3 . The electrochemical cell of claim 2 , wherein the cathode comprises lithium and the reactive film comprises an oxide of at least one metal or semimetal selected from the group consisting of B, Ti, Zr, Nb, Zn, Al, Ga, In, and Sn; and the metal oxide optionally also comprises lithium ions.

4 . The electrochemical cell of claim 1 , wherein the reactive film of the anode has a three-dimensional, non-planar morphology.

5 . A rechargeable lithium electrochemical cell comprising, in a fully discharged state: a cathode comprising lithium and a layered anode with a lithium electrolyte therebetween; wherein the layered anode comprises a metal substrate and a metal or semimetal film having a thickness of about 1 nm to about 100 nm on a surface of the substrate in contact with the electrolyte; wherein the film comprises at least one elemental metal or semimetal selected from the group consisting of B, Mg, Al, Ca, Zn, Ga, Ge, As, Sr, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, Ir, Pt, Au, Hg, Tl, Pb, and Bi; the film alloys with, or forms a mixed phase with, lithium from the cathode during charging of the cell, and releases the lithium back to the cathode during discharging of the cell to reconstitute the film.

6 . The electrochemical cell of claim 5 , wherein the substrate of the anode is a copper foil or mesh.

7 . The electrochemical cell of claim 5 , wherein the film comprises at least one metal selected from the group consisting of Mg, Al, Ga, Sn, In, Ag, Au, Pt, Zn, Pb, and Bi.

8 . The electrochemical cell of claim 5 , wherein the film comprises at least one metal selected from the group consisting of Al, Au, and Pt.

9 . The electrochemical cell of claim 5 , wherein the film additionally comprises at least some lithium.

10 . The electrochemical cell of claim 5 , wherein the lithium electrolyte is a liquid electrolyte comprising a lithium electrolyte salt in a non-aqueous aprotic solvent; the electrochemical cell further comprises a porous separator between the cathode and the anode; and the separator is immersed in, and permeable to, the liquid electrolyte.

11 . The electrochemical cell of claim 5 , wherein the lithium electrolyte is a polymer electrolyte comprising a lithium electrolyte salt dispersed in a polymer matrix.

12 . The electrochemical cell of claim 11 , wherein the polymer electrolyte further comprises a non-aqueous aprotic solvent dispersed in the polymer matrix.

13 . The electrochemical cell of claim 5 , wherein the metal or semimetal film of the anode has a three-dimensional, non-planar morphology.

14 . A rechargeable lithium electrochemical cell comprising, in a fully discharged state: a cathode comprising lithium and a layered anode with a lithium electrolyte therebetween; wherein the layered anode comprises a metal substrate and a lithium-reactive oxide film having a thickness of about 1 nm to about 100 nm on a surface of the substrate in contact with the electrolyte; wherein the oxide film comprises an oxide of a metal or a semimetal selected from the group consisting of Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Y, Zr, Nb, Mo, In, Sn, Sb, Te, La, Ce, Hf, Ta, W, Pb, and Bi; the film reacts with lithium from the cathode during charging of the cell, and releases the lithium back to the cathode to reconstitute the metal oxide film during discharging of the cell.

15 . The electrochemical cell of claim 14 , wherein the substrate of the anode is a copper foil or mesh.

16 . The electrochemical cell of claim 14 , wherein the lithium-reactive oxide film comprises an oxide of at least one metal or semimetal selected from the group consisting of B, Ti, Zr, Nb, Zn, Al, Ga, In, and Sn.

17 . The electrochemical cell of claim 14 , wherein the metal oxide or semimetal oxide also comprises lithium ions.

18 . The electrochemical cell of claim 17 , wherein the film comprises a lithium aluminum oxide.

19 . The electrochemical cell of claim 14 , wherein the lithium electrolyte is a liquid electrolyte comprising a lithium electrolyte salt in a non-aqueous aprotic solvent; the electrochemical cell further comprises a porous separator between the cathode and the anode; and the separator is immersed in, and permeable to, the liquid electrolyte.

20 . The electrochemical cell of claim 14 , wherein the lithium electrolyte is a polymer electrolyte comprising a lithium electrolyte salt dispersed in a polymer matrix.

21 . The electrochemical cell of claim 20 , wherein the polymer electrolyte further comprises a non-aqueous aprotic solvent dispersed in the polymer matrix.

22 . The electrochemical cell of claim 14 , wherein the oxide film of the anode has a three-dimensional, non-planar morphology.

Assignees

• Uchicago Argonne Llc

Inventors

• Counihan Michael J
• Tepavcevic Sanja
• Barai Pallab
• Srinivasan Venkat
• Mane Anil U
• Pathak Rajesh
• Elam Jeffrey W

Classifications

• H01M4/38

  of elements or alloys · CPC title

• H01M4/1395

  of electrodes based on metals, Si or alloys · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title