Methods for improving critical current density in a sulfide-based all-solid-state lithium-ion battery

Patent metadata

Field	Value
Publication number	US-12412925-B1
Application number	US-202418946564-A
Country	US
Kind code	B1
Filing date	Nov 13, 2024
Priority date	Apr 30, 2024
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

Solid electrolyte compositions and solid-state batteries are disclosed, which comprise a solid electrolyte layer including a sulfide-containing solid-state electrolyte material and a compound of Chemical Formula 1. The sulfide-containing solid-state electrolyte material includes but is not limited to Li 6 PS 5 Cl (“LPSC”), an LPS-based glass or glass ceramic of formula xLi 2 S·yP 2 S 5 , wherein x+y=1, or an argyrodite-based sulfide-based solid electrolyte or formula Li 6 PS 5 X, wherein X═Cl, Br, or I) or Li 6-y PS 5-y Cl 1+y , where y is <1. In some aspects, the compound of Chemical Formula 1 is sodium 3-mercapto-1-propanesulfonate (3M1P).

First claim

What is claimed is:

1. A solid electrolyte composition comprising:
a sulfide-containing solid electrolyte material, having a surface; and
an organic coating, wherein the organic coating is formed on the surface of the sulfide-containing solid-state electrolyte material, and
wherein the coating is formed from at least one compound of Chemical Formula 1 and the sulfide-containing solid-state electrolyte material:
A—R—W  Chemical Formula 1

wherein:
A is a halogen;
R is a substituted or unsubstituted C3-C20 alkylene group; and
W is a sulfonate, a phosphonate, or a salt thereof.

2. The solid electrolyte composition according to claim 1 , wherein the compound of Chemical Formula 1 is attached to the surface of the sulfide-containing solid-state electrolyte material by chemisorption, van der Waals interaction, or ionic interaction.

3. The solid electrolyte composition according to claim 1 , wherein the compound of Chemical Formula 1 reacts with the sulfide-containing solid-state electrolyte material to form a covalent bond.

4. The solid electrolyte composition according to claim 1 , wherein in the compound of Chemical Formula 1, A is fluoride, chloride, bromide, or iodide.

5. The solid electrolyte composition according to claim 1 , wherein in the compound of Chemical Formula 1, R is a C6-C16 alkylene group.

6. The solid electrolyte composition according to claim 1 , wherein the compound of Chemical Formula 1 has a total of 6 to 16 carbons.

7. The solid electrolyte composition according to claim 1 , wherein in the compound of Chemical Formula 1, at least one of R is a substituted C3-C20 alkylene group, wherein there are one or more substituents selected from fluorine, chlorine, bromine, ester or ketone moieties.

8. The solid electrolyte composition according to claim 1 , wherein the compound of Chemical Formula 1 is 3-chloro-1-propanesulfonic acid or a salt thereof.

9. The solid electrolyte composition according to claim 1 , wherein the sulfide-containing solid electrolyte material is selected from the group consisting of an inorganic-based electrolyte material and an organic-based electrolyte material.

10. The solid electrolyte composition according to claim 1 , wherein the sulfide-containing solid electrolyte comprises at least one selected from Li 3 P 7 S 11 , Li 10 GeP 2 Si 2 , and Na 3 PS 4 and/or Li 6 PS 5 Cl.

11. The solid electrolyte composition according to claim 1 , wherein the sulfide-containing solid electrolyte comprises at least one selected from LPS-based glass or glass ceramic of formula xLi 2 S·yP 2 S 5 , wherein x+y=1.

12. The solid electrolyte composition according to claim 1 , wherein the sulfide-containing solid electrolyte comprises an argyrodite-based solid electrolyte of formula Li 6 PS 5 X, wherein X is Cl, Br, or I.

13. The solid electrolyte composition according to claim 1 , wherein the sulfide-containing solid electrolyte comprises an argyrodite-based solid electrolyte of formula Li 6-y PS 5-y Cl 1+y , where y is <1.

14. A method for making a solid electrolyte, comprising:
providing a sulfide-containing solid electrolyte material;
reacting the solid electrolyte material with at least one compound of Chemical Formula 1 to form a coated sulfide-containing solid electrolyte material; and
using the coated sulfide-containing solid electrolyte material to form a solid electrolyte:
A—R—W  Chemical Formula 1

wherein:
A is a halogen;
R is a substituted or unsubstituted C3-C20 alkylene group; and
W is a sulfonate, a phosphonate, or a salt thereof.

15. An all-solid-state battery comprising:
a negative electrode,
a positive electrode; and
a solid electrolyte comprising the solid electrolyte composition according to claim 1 , wherein the solid electrolyte is interposed between the negative electrode and the positive electrode.

16. The all-solid-state battery according to claim 15 , wherein the negative electrode comprises lithium crystals in a hexagonal close-packed (HCP) structure.

17. The all-solid-state battery according to claim 15 , wherein the deposited lithium crystals are oriented with their (0001) facet parallel to the substrate.

18. An all-solid state lithium metal battery comprising:
a negative electrode comprising lithium,
a positive electrode;
a solid electrolyte composition interposed between the negative electrode and the positive electrode,
wherein the negative electrode comprises lithium crystals in a hexagonal close-packed (HCP) structure;
wherein the solid electrolyte composition comprises:
a sulfide-containing solid electrolyte material; and
an organic coating, wherein the organic coating is formed on the surface of the sulfide-containing solid-state electrolyte material, and
wherein the coating is formed from at least one compound of Chemical Formula 1 and the sulfide-containing solid-state electrolyte material:
A—R—W  Chemical Formula 1

wherein:
A is a halogen, a SH group, a triethoxysilyl group or a trimethoxysilyl group;
R is a substituted or unsubstituted C3-C20 alkylene group; and
W is a sulfonate, a phosphonate, or a salt thereof.

19. An electric vehicle comprising the all-solid-state battery according to claim 18 .

20. An electric vehicle according to claim 19 , wherein the electric vehicle is selected from an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), an electric motorcycle, an electric bike (E-bike), an electric scooter (E-scooter) or an electric golf cart.

Assignees

• Lg Energy Solution Ltd
• Univ California
• The Regents Of The Univeristy Of California

Inventors

• Liu Ping
• Zhou Ke
• Liu Mengchen
• Oh Jeong Woo
• Song Min-Sang

Classifications

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0562

  Solid materials · CPC title

• H01M2300/0068

  inorganic · CPC title