Lithium ion conducting protective film and method of use

Patent metadata

Field	Value
Publication number	US-12388134-B2
Application number	US-202217980682-A
Country	US
Kind code	B2
Filing date	Nov 4, 2022
Priority date	Jun 19, 2013
Publication date	Aug 12, 2025
Grant date	Aug 12, 2025

Abstract

A lithium ion conducting protective film produced using a layer-by-layer assembly process. The lithium ion conducting protective film is assembled on a substrate by a sequential exposure of the substrate to a first poly(ethylene oxide) (PEO) layer including a cross-linking silane component on the first side of the substrate, a graphene oxide (GO) layer on the first PEO layer, a second poly(ethylene oxide) (PEO) layer including a cross-linking silane component on the GO layer and a poly(acrylic acid) (PAA) layer on the second PEO layer. The film functions as a lithium ion conducting protective film that isolates the lithium anode from the positive electrochemistry of the cathode in a lithium-air battery, thereby preventing undesirable lithium dendrite growth.

First claim

What is claimed is:

1. A method of preparing a lithium-air electrochemical cell, the method comprising:
preparing a lithium ion conducting protective film;
disposing a lithium conducting electrolyte between an anode comprising lithium and an oxygen gas diffusive cathode; and
disposing the lithium ion conducting protective film between the anode and the electrolyte,
wherein preparing the lithium ion conducting protective film comprises:
providing a lithium anode protective layer comprising a graphene oxide layer;
providing a lithium ion conductive layer; and
introducing a cross-linking component to cross-link between the lithium anode protective layer and the lithium ion conductive layer of the lithium ion conducting protective film;
disposing at least one tetralayer on a first side of a substrate, wherein disposing at the at least one tetralayer further comprises:
disposing a first poly (ethylene oxide) (PEO) layer including the cross-linking component on the first side of the substrate;
disposing the graphene oxide (GO) layer on the first PEO layer;
disposing a second poly (ethylene oxide) (PEO) layer including the cross-linking component on the GO layer; and
disposing a poly (acrylic acid) (PAA) layer on the second PEO layer.

2. The method of claim 1 , wherein disposing the first poly (ethylene oxide) (PEO) layer including the cross-linking component on the first side of the substrate further comprising, exposing the substrate to a poly (ethylene oxide) (PEO) solution including the cross-linking component.

3. The method of claim 2 , wherein preparing the lithium ion conducting protective film further comprises dissolving the cross-linking component in the poly (ethylene oxide) (PEO) solution prior to exposing the substrate to the poly (ethylene oxide) (PEO) solution.

4. The method of claim 2 , wherein preparing the lithium ion conducting protective film further comprises dissolving lithium bis(oxalate) borate in the poly (ethylene oxide) (PEO) solution prior to exposing the substrate to the poly (ethylene oxide) (PEO) solution including a cross-linking component.

5. The method of claim 1 , wherein disposing the graphene oxide (GO) layer on the first PEO layer further comprises, exposing the first PEO layer to a graphene oxide solution.

6. The method of claim 1 , wherein disposing the second poly (ethylene oxide) (PEO) layer including the cross-linking component on the GO layer further comprises, exposing the GO layer to the poly (ethylene oxide) (PEO) solution including the cross-linking component.

7. The method of claim 1 , wherein disposing a poly (acrylic acid) (PAA) layer on the second PEO layer further comprises, exposing the second PEO layer to a poly (acrylic acid) (PAA) solution.

8. The method of claim 7 , further comprising dissolving lithium bis(oxalate) borate in the poly (acrylic acid) (PAA) solution prior to exposing the second PEO layer to a poly (acrylic acid) (PAA) solution.

9. The method of claim 1 , further comprising disposing a plurality of tetralayers on the first side of the substrate.

10. The method of claim 1 , wherein the cross-linking component is selected from the group consisting of monofunctional silane, bifunctional silane, multifunctional silane, trialkoxysilane and trichlorosilane.

11. The method of claim 1 , wherein preparing the lithium ion conducting protective film comprises crosslinking Si-O to graphene oxide.

12. The method of claim 1 , wherein the cross-linking component comprises a polyelectrolyte containing amide groups formed by the reaction of amine or diamine functional groups with carboxylic acid functional group.

13. The method of claim 1 , wherein the oxygen gas diffusive cathode comprises porous carbon.

14. The method of claim 1 , wherein the lithium conducting electrolyte is an aqueous electrolyte.

15. The method of claim 1 , wherein the lithium conducting electrolyte is a non-aqueous electrolyte.

16. The method of claim 1 , wherein the lithium conducting electrolyte comprises dimethoxyethane-lithium bis(trifluoromethanesulfonyl) imide.

Assignees

• Samsung Electronics Co Ltd
• Massachusetts Inst Technology

Inventors

• Khiterer Mariya
• Hammond Paula T
• Lee Sun Hwa

Classifications

• H01M50/411

  Organic material · CPC title

• H01M50/409

  Separators, membranes or diaphragms characterised by the material · CPC title

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• H01M50/431

  Inorganic material · CPC title

• H01M50/457

  comprising three or more layers · CPC title