IP Library › Granted Patent US 12,394,823
Granted Patent B2
US 12,394,823 · App. 17/675,839 · Granted Aug 19, 2025

Polymer electrolytes for electrochemical cells

Inventors: Yang Shao-Horn (Newton, MA); Jeremiah A. Johnson (Boston, MA); Jeffrey Lopez (Cambridge, MA); Teruhiko Saito (Osaka, JP); Megan Hill (Cambridge, MA); Sipei Li (East Boston, MA)
Assignee: Massachusetts Institute of Technology
H01M10/0565H01M2300/0082
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Quick Facts
Patent No.
US 12,394,823
App. No.
17/675,839
Granted
Aug 19, 2025
Kind
B2
Abstract

The present disclosure provides solid-state electrolytes based on a borylated-polymers (e.g., borylated-polybutadiene). Further provided are kits comprising, methods of synthesizing, and methods of using the solid-state electrolytes. In some aspects, the solid-state electrolytes demonstrate high ion conductivity at room temperature.

Claims (58)

1. A solid-state electrolyte comprising an ion and a polymer, wherein the polymer comprises repeat units comprising alkylene and boronyl moieties.

2. The solid-state electrolyte of claim 1 , wherein the polymer further comprises alkenylene moieties.

3. The solid-state electrolyte of claim 1 , wherein the polymer is a polybutadiene polymer.

4. The solid-state electrolyte of claim 1 , wherein the polymer comprises:

terminal methyl groups,

repeat unit Z, which is of the formula:

 or a salt thereof;

repeat unit X, which is of the formula:

 or a salt thereof; and

repeat unit Y, which is of the formula:

wherein

each R 1 is independently C 1-20 alkyl, —OR 2 , heteroC 1-20 alkyl, C 3-10 carbocyclyl, or 3-14 membered heterocyclyl, or two R 1 groups on the same boron are joined to form a 3-14 membered, monocyclic, bicyclic, or tricyclic, heterocyclyl moiety; and

each R 2 is independently C 1-20 alkyl, heteroC 1-20 alkyl, C 3-10 carbocyclyl, 3-14 membered heterocyclyl, C 6-14 aryl, or 5-14 membered heteroaryl.

5. The solid-state electrolyte of claim 4 , wherein the molar ratio of repeat unit Z to repeat unit X is from about 9:2 to about 1:2.

6. The solid-state electrolyte of claim 4 , wherein the molar ratio of repeat unit X to repeat unit Y is from about 9:1 to about 2:9.

7. The solid-state electrolyte of claim 4 , wherein the ratio of repeat unit Z to repeat unit X to repeat unit Y is about 11:4:5, about 3:2:5, or about 15:4:1.

8. The solid-state electrolyte of claim 1 , wherein the polymer comprises:

terminal methyl groups,

repeat unit Z, which is of the formula:

 or a salt thereof; and

repeat unit X, which is of the formula:

 or a salt thereof;

wherein

each R 1 is independently C 1-20 alkyl, —OR 2 , heteroC 1-20 alkyl, C 3-10 carbocyclyl, or 3-14 membered heterocyclyl, or two R 1 groups on the same boron are joined to form a 3-14 membered, monocyclic, bicyclic, or tricyclic, heterocyclyl moiety; and

each R 2 is independently C 1-20 alkyl, heteroC 1-20 alkyl, C 3-10 carbocyclyl, 3-14 membered heterocyclyl, C 6-14 aryl, or 5-14 membered heteroaryl.

9. The solid-state electrolyte of claim 8 , wherein the molar ratio of repeat unit Z to repeat unit X is about 8:2.

10. The solid-state electrolyte of claim 4 , wherein:

each R 1 is C 1-20 alkyl.

11. The solid-state electrolyte of claim 4 , wherein:

two R 1 groups on the same boron are joined to form a 3-14 membered, monocyclic, bicyclic, or tricyclic, heterocyclyl moiety.

12. The solid-state electrolyte of claim 4 , wherein —B(R 1 ) 2 is of the formula:

13. The solid-state electrolyte of claim 1 , wherein the ion is Li + , Na + , K + , Ag + , Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , or O 2− .

14. The solid-state electrolyte of claim 1 , wherein the weight percent percentage of the ion is between about 5% and about 70%.

15. A method of preparing a solid-state electrolyte of claim 1 comprising hydroborating polybutadiene with a borane or organoborane to yield a borylated-polybutadiene.

16. A solid-state electrolyte of claim 1 made by a process comprising the steps of:

hydroborating polybutadiene with a borane or organoborane to yield a borylated-polybutadiene;

mixing the borylated-polybutadiene and an ion in a solvent; and

forming a film.

17. An electrochemical cell comprising the solid-state electrolyte of claim 1 .

18. A method of transporting ions comprising contacting the solid-state electrolyte of claim 1 with ions.

19. A method of conducting electrical charge comprising contacting the solid-state electrolyte of claim 1 with ions.

20. The solid-state electrolyte of claim 4 , wherein R 1 is C 1-8 alkyl.

21. The solid-state electrolyte of claim 4 , wherein R is of the formula:

22. The solid-state electrolyte of claim 4 , wherein the ion is Lit.

23. The solid-state electrolyte of claim 22 , wherein:

(i) the molar ratio of repeat unit X to repeat unit Z to repeat unit Y is 1:4:0, and the molar ratio of Li + to boron is 0.5;

(ii) the molar ratio of repeat unit X to repeat unit Z to repeat unit Y is 4:11:5, and the molar ratio of Li + to boron is 0.5;

(iii) the molar ratio of repeat unit X to repeat unit Z to repeat unit Y is 2:3:5, and the molar ratio of Li + to boron is 0.5; or

(iv) the molar ratio of repeat unit X to repeat unit Z to repeat unit Y is 4:1:15, and the molar ratio of Li + to boron is 0.5.

24. The solid-state electrolyte of claim 8 , wherein two R 1 groups on the same boron are joined to form a 3-14 membered, monocyclic, bicyclic, or tricyclic, heterocyclyl moiety.

25. The solid-state electrolyte of claim 8 , wherein —B(R 1 ) 2 is of the formula:

26. The solid-state electrolyte of claim 8 , wherein —B(R 1 ) 2 is of the formula:

or

27. The solid-state electrolyte of claim 8 , wherein the molar ratio of repeat unit Z to repeat unit X is from about 9:2 to about 1:2.

28. The solid-state electrolyte of claim 8 , wherein the ion is Lit.

29. The solid-state electrolyte of claim 8 , wherein the weight percentage of the ion is between about 5% and about 70%.

30. The solid-state electrolyte of claim 1 , wherein the weight-average molecular weight of the polymer is about 5000 g/mol, about 5100 g/mol, or about 5150 g/mol.

31. The solid-state electrolyte of claim 1 , wherein the solid-state electrolyte has a conductivity of 10 −9 to 10 −4 S/cm at 25° C.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 24, 2023
From: SHAO-HORN, YANG; JOHNSON, JEREMIAH A.; LOPEZ, JEFFREY; SAITO, TERUHIKO; HILL, MEGAN; LI, SIPEI
To: MASSACHUSETTS INSTITUTE OF TECHNOLOGY
Reel/Frame 064691/0093 →
Continuity (2)
Provisional Application 63151167 · Feb 19, 2021
Related Publication 20220271337A1 · Aug 25, 2022
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