Borate salts, polymers and composites

Patent metadata

Field	Value
Publication number	US-11649358-B2
Application number	US-201916567647-A
Country	US
Kind code	B2
Filing date	Sep 11, 2019
Priority date	Sep 11, 2019
Publication date	May 16, 2023
Grant date	May 16, 2023

Abstract

Described herein are borate salts useful as additives, binders, and electrolyte salts for solid state lithium ion batteries. In particular, the borate salts of Formula (I), Formula (II) and Formula (III) as described herein:can be polymerized, or can be bound to an existing polymer, to provide polymeric binders for ceramic solid state electrolytes that are themselves capable of ion transport independent of the ceramic.

First claim

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

1. A single-ion conducting polymer-ceramic composite comprising particles of a lithium ion conducting ceramic in matrix of a single-ion conducting polymer; wherein the single-ion conducting polymer is formed by polymerization of a bis(2-allyl-2-fluoromalonato)borate salt in the presence of a cross-linking co-monomer comprising trimethylolpropane tris(3-mercaptopropionate) initiated by exposing the precursor mixture to ultraviolet light.

2. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the polymerization is conducted in the presence of 4-dimethylaminopyridine.

3. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the polymerization is conducted in the presence of the particles of the lithium ion conducting ceramic.

4. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the lithium ion conducting ceramic comprises at least one material selected from the group consisting of a metal oxide, a metal phosphate, a metal sulfide, and a metal oxide-sulfide.

5. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the lithium ion conducting ceramic comprises a lithium-lanthanum-zirconium oxide material.

6. The single-ion conducting polymer-ceramic composite of claim 5 , wherein the lithium-lanthanum-zirconium oxide material is Li 7 La 3 Zr 2 O 12 .

7. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the lithium ion conducting ceramic comprises LiTi 2 (PO 4 ) 3 .

8. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the lithium ion conducting ceramic comprises at least one metal sulfide selected from the group consisting of Li 3 PS 4 , Li 4 GePS 4 , Li 11 P 2 GeS 12 , Li 9.6 P 3 S 12 , Li 10 GeP 2 S 12 , Li 10.35 Ge 1.35 P 1.65 S 12 , and Li 9.81 Sn 0.81 P 2.19 S 12 .

9. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the lithium ion conducting ceramic comprises at least one metal oxide-sulfide selected from the group consisting of Li 9 P 3 S 903 and Li 9.42 Si 1.03 P 2.1 S 9.96 O 2.04 .

10. The single-ion conducting polymer-ceramic composite of claim 1 , wherein the bis(2-allyl-2-fluoromalonato)borate salt is lithium bis(2-allyl-2-fluoromalonato)borate.

11. A single-ion conducting polymer-ceramic composite comprising particles of a lithium ion conducting ceramic in matrix of a single-ion conducting polymer; wherein the single-ion conducting polymer is formed by ultraviolet light initiated polymerization of lithium bis(2-allyl-2-fluoromalonato)borate in the presence of trimethylolpropane tris(3-mercaptopropionate) and 4-dimethylaminopyridine.

12. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the polymerization is conducted in the presence of the particles of the lithium ion conducting ceramic.

13. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the lithium ion conducting ceramic comprises at least one material selected from the group consisting of a metal oxide, a metal phosphate, a metal sulfide, and a metal oxide-sulfide.

14. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the lithium ion conducting ceramic comprises a lithium-lanthanum-zirconium oxide material.

15. The single-ion conducting polymer-ceramic composite of claim 14 , wherein the lithium-lanthanum-zirconium oxide material is Li 7 La 3 Zr 2 O 12 .

16. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the lithium ion conducting ceramic comprises LiTi 2 (PO 4 ) 3 .

17. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the lithium ion conducting ceramic comprises at least one metal sulfide selected from the group consisting of Li 3 PS 4 , Li 4 GePS 4 , Li 11 P 2 GeS 12 , Li 9.6 P 3 Su, Li 10 GeP 2 S 12 , Li 10.35 Ge 1.35 P 1.65 S 12 , and Li 9.81 Sn 0.81 P 2.19 S 12 .

18. The single-ion conducting polymer-ceramic composite of claim 11 , wherein the lithium ion conducting ceramic comprises at least one metal oxide-sulfide selected from the group consisting of Li 9 P 3 S 9 O 3 and Li 9.42 Si 1.03 P 2.1 S 9.9602.04 .

Assignees

• Uchicago Argonne Llc

Inventors

• Liao Chen
• Dzwiniel Trevor L
• Liu Kewel

Classifications

• H01M10/0525

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

• C08K2003/2203

  of lithium · CPC title

• C08K3/22

  of metals · CPC title

• C08L85/04 Primary

  containing boron · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title