Method to protect a lithium metal anode in a rechargeable lithium metal battery

Patent metadata

Field	Value
Publication number	US-12009511-B2
Application number	US-202217676019-A
Country	US
Kind code	B2
Filing date	Feb 18, 2022
Priority date	Feb 18, 2022
Publication date	Jun 11, 2024
Grant date	Jun 11, 2024

Abstract

A rechargeable metal halide battery fabricated with a liquid nitrogen treated metallic anode demonstrates a stable cycle life with a slow rate of degradation and high discharge capacity in comparison to battery cells with untreated anodes. The anode, which may be an alkali metal and/or an alkaline earth metal, is pretreated with the liquid nitrogen prior to formation in a battery stack. The liquid nitrogen treatment forms a metal nitride on a surface of the anode that (i) increases the surface area of the anode, (ii) acts as a passivation layer that prevents detrimental SEI-forming side reactions that degrade anodes, and (iii) suppresses dendrite growth. Where the anode is lithium, the metal nitride is lithium nitride (Li3N).

First claim

We claim:

1. A method of fabricating a battery comprising:
forming a battery stack comprising a metallic anode treated for 1-100 seconds with liquid nitrogen to form a passivation layer comprising a nitrogen-containing compound on a surface of the metallic anode, a cathode, and an electrolyte comprising at least one ion-conducting material, wherein the electrolyte is in physical contact with the anode and the cathode.

2. The method of claim 1 , wherein the metallic anode is treated with the liquid nitrogen for 10-80 seconds.

3. The method of claim 1 , wherein the metallic anode is dipped in liquid nitrogen prior to the forming of the battery stack.

4. The method of claim 1 , wherein the nitrogen-containing compound is metal nitride.

5. The method of claim 1 , wherein the passivation layer increases the surface area of the anode and suppresses dendrite growth on the anode surface.

6. The method of claim 1 , wherein the passivation layer further comprises a metal oxide, wherein the concentration of the nitrogen-containing compound in the passivation layer is higher than the concentration of the metal oxide.

7. The method of claim 1 , wherein the metallic anode comprises at least one alkali metal and/or at least one alkaline earth metal.

8. The method of claim 1 , wherein the metallic anode comprises a metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), and combinations thereof.

9. The method of claim 1 , wherein the cathode is an intercalation cathode and/or a conversion cathode.

10. The method of claim 1 , wherein the cathode comprises a metal halide incorporated into an electrically conductive material.

11. The method of claim 10 , wherein the metal halide comprises a metal ion and a halide ion, wherein the metal ion is selected from one or more of Li + , Mg + , Zn + , Al + , and Na + and the halide ion is selected from one or more of I − , Br − , Cl − , and F − .

12. The method of claim 10 , wherein the electrically conductive material is a carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, graphite, graphene, graphene oxide, and combinations thereof.

13. The method of claim 1 , wherein the at least one ion-conducting material is a lithium salt selected from the group consisting of lithium nitrate (LiNO 3 ), lithium fluoride (LiF), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI; LiC 2 F 6 NO 4 S 2 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium hexafluorophosphate (LiPF 6 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium bis(oxalate)borate (LiBOB), and combinations thereof.

14. The method of claim 1 , wherein the electrolyte further comprises an organic solvent selected from the group consisting of nitriles, ethers, carbonates, heterocyclic compounds, glymes, and combinations thereof.

15. The method of claim 1 , wherein the electrolyte further comprises an oxidizing gas selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and combinations thereof.

16. A method of fabricating a battery comprising:
pre-treating a lithium anode for 1-100 seconds with liquid nitrogen to form a lithium nitride passivation layer on a surface of the anode; and
forming a battery stack comprising the pre-treated lithium anode, a cathode comprising a metal halide incorporated into an electrically conductive material, and an electrolyte comprising at least one organic solvent and at least one ion-conducting material, wherein the electrolyte is in physical contact with the anode and the cathode.

17. The method of claim 16 , wherein the lithium nitride passivation layer increases the surface area of the anode and suppresses dendrite growth on anode surface.

18. The method of claim 16 , wherein the cathode is an intercalation cathode and/or a conversion cathode.

19. The method of claim 16 , wherein the electrolyte further comprises an oxidizing gas selected from the group consisting of oxygen, air, nitric oxide, nitrogen dioxide, and combinations thereof.

Assignees

• IBM

Inventors

• Kim Yumi
• Pandian Amaresh Samuthira
• Bui Holt
• Kim Jangwoo
• Na Young-Hye

Classifications

• H01M4/625

  Carbon or graphite · CPC title

• H01M10/058

  Construction or manufacture · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M2300/0054

  Halogenides · CPC title

• H01M4/388

  Halogens · CPC title