Gel electrolytes and the manufacture thereof
Provided herein are a variety of electrolytes, electrolyte systems, and separator systems, as well as batteries comprising the same and precursors thereof. In specific embodiments are semi-solid or gel electrolytes, particularly those prepared using (i) a cross-linkable polysilsesquioxane with high ionic conductivity and (ii) a liquid electrolyte (e.g., ionic liquid).
1. A semi-solid electrolyte system comprising (i) a polysilsesquioxane, and (ii) a liquid electrolyte, the polysilsesquioxane being at least partially crosslinked to form a three-dimensional matrix, the liquid electrolyte being configured within the three-dimensional matrix, and wherein the polysilsesquioxane is:
functionalized by one or more functional groups with high ionic conductivity.
2. The electrolyte system of claim 1 , wherein the polysilsesquioxane is a ladder-like polysilsesquioxane (LPSQ) or a polyhedral oligomeric polysilsesquioxane (PSSQ).
3. The electrolyte system of claim 1 , wherein the polysilsesquioxane is functionalized by one or more cross-linked or cross-linkable functional groups or by one or more functional group comprising polymerized alkylene or epoxide group.
4. The electrolyte system of claim 1 , wherein the polysilsesquioxane is ladder-like poly(polyoxoalkylene-co-(alk)acryloxyalkyl) silsesquioxane or is ladder-like poly(polyethyleneoxide-co-methacryloxypropyl) silsesquioxane (LPEOMASQ).
5. The electrolyte system of claim 1 , wherein the electrolyte is an ionic liquid.
6. The electrolyte system of claim 1 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:99 to about 99:1.
7. The electrolyte system of claim 1 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:10 to about 10:1.
8. The electrolyte system of claim 1 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:3 to about 3:1.
9. The electrolyte system of claim 1 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:1.
10. The electrolyte system of claim 1 , wherein the semi-solid is a gel.
11. The electrolyte system of claim 1 , wherein the weight ratio of the liquid electrolyte to the polysilsesquioxane is at least 10:1.
12. A separator system comprising
a. a semi-solid electrolyte of claim 1 ; and
b. a porous membrane, the semi-solid electrolyte being configured within the three-dimensional matrix.
13. The separator system of claim 12 , wherein the separator system is a battery separator system, a lithium battery separator system, a lithium ion battery separator system, or a lithium sulfur battery separator system.
14. The separator system of claim 12 , wherein the porous membrane is a polymer-ceramic composite or hybrid membrane.
15. A compound of the following formula:
wherein,
R 1 and R 2 are independently selected from H, alkyl, and heteroalkyl, and are optionally substituted by oxo, alkoxy, or a combination thereof, wherein R 1 is heteroalkyl or R 2 is heteroalkyl, or both R 1 and R 2 are heteroalkyl;
R 3 and R 4 are independently selected from H, alkyl, heteroalkyl, alkylaryl, alkylarylalkyl, heteroalkylaryl, and heteroalkylarylalkyl, and are optionally substituted by oxo, alkoxy, or a combination thereof; and
m and n are integers.
16. The compound of claim 15 , wherein
R 3 is alkyl, heteroalkyl, alkylaryl, alkylarylalkyl, heteroalkylaryl, or heteroalkylarylalkyl;
R 3 is optionally substituted by oxo, alkoxy, or a combination thereof; and
R 3 comprises at least one point of carbon-carbon unsaturation.
17. The electrolyte system of claim 1 , wherein the polysilsesquioxane is functionalized by one or more polymerized acryloylalkyl, methacryloylalkyl, ethacryloylalkyl, acryloylheteroalkyl, methacryloylalkyl, or ethacryloylalkyl, or any combination thereof.
18. A semi-solid electrolyte system comprising (i) a polysilsesquioxane, and (ii) a liquid electrolyte, the polysilsesquioxane being at least partially crosslinked to form a three-dimensional matrix, the liquid electrolyte being configured within the three-dimensional matrix, and wherein the polysilsesquioxane is:
functionalized by one or more heteroalkyl group.
19. The electrolyte system of claim 18 , wherein the polysilsesquioxane is a ladder-like polysilsesquioxane (LPSQ) or a polyhedral oligomeric polysilsesquioxane (PSSQ).
20. The electrolyte system of claim 18 , wherein the polysilsesquioxane is functionalized by one or more cross-linked or cross-linkable functional groups or by one or more functional group comprising polymerized alkylene or epoxide group.
21. The electrolyte system of claim 18 , wherein the polysilsesquioxane is ladder-like poly(polyoxoalkylene-co-(alk)acryloxyalkyl) silsesquioxane or is ladder-like poly(polyethyleneoxide-co-methacryloxypropyl) silsesquioxane (LPEOMASQ).
22. The electrolyte system of claim 18 , wherein the electrolyte is an ionic liquid.
23. The electrolyte system of claim 18 , wherein the heteroalkyl group is a poly(oxoalkylene).
24. The electrolyte system of claim 18 , wherein the semi-solid is a gel.
25. The electrolyte system of claim 18 , wherein the weight ratio of the liquid electrolyte to the polysilsesquioxane is at least 10:1.
26. The electrolyte system of claim 18 , wherein the polysilsesquioxane is functionalized by one or more polymerized acryloylalkyl, methacryloylalkyl, ethacryloylalkyl, acryloylheteroalkyl, methacryloylalkyl, or ethacryloylalkyl, or any combination thereof.
27. A semi-solid electrolyte system comprising (i) a polysilsesquioxane, and (ii) a liquid electrolyte, the polysilsesquioxane being at least partially crosslinked to form a three-dimensional matrix, the liquid electrolyte being configured within the three-dimensional matrix, and wherein the polysilsesquioxane is:
functionalized by one or more polymerized acryloylalkyl, methacryloylalkyl, ethacryloylalkyl, acryloylheteroalkyl, methacryloylalkyl, or ethacryloylalkyl, or any combination thereof.
28. The electrolyte system of claim 27 , wherein the polysilsesquioxane is a ladder-like polysilsesquioxane (LPSQ) or a polyhedral oligomeric polysilsesquioxane (PSSQ).
29. The electrolyte system of claim 27 , wherein the polysilsesquioxane is ladder-like poly(polyoxoalkylene-co-(alk)acryloxyalkyl) silsesquioxane or is ladder-like poly(polyethyleneoxide-co-methacryloxypropyl) silsesquioxane (LPEOMASQ).
30. The electrolyte system of claim 27 , wherein the electrolyte is an ionic liquid.
31. The electrolyte system of claim 27 , wherein the polysilsesquioxane is functionalized by one or more functional groups with high ionic conductivity.
32. The electrolyte system of claim 27 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:99 to about 99:1.
33. The electrolyte system of claim 27 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:10 to about 10:1.
34. The electrolyte system of claim 27 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:3 to about 3:1.
35. The electrolyte system of claim 27 , wherein the number ratio of cross-linked or cross-linkable functional groups to functional groups with high ionic conductivity is about 1:1.
36. The electrolyte system of claim 27 , wherein the one or more functional groups with high ionic conductivity is/are heteroalkyl group(s).
37. The electrolyte system of claim 34 , wherein the heteroalkyl group is a poly(oxoalkylene).
38. The electrolyte system of claim 27 , wherein the semi-solid is a gel.
39. The electrolyte system of claim 27 , wherein the weight ratio of the liquid electrolyte to the polysilsesquioxane is at least 10:1.
40. A separator system comprising
a. a semi-solid electrolyte of claim 18 ; and
b. a porous membrane, the semi-solid electrolyte being configured within the three-dimensional matrix.
41. The separator system of claim 40 , wherein the separator system is a battery separator system, a lithium battery separator system, a lithium ion battery separator system, or a lithium sulfur battery separator system.
42. The separator system of claim 40 , wherein the porous membrane is a polymer-ceramic composite or hybrid membrane.
43. A separator system comprising
a. a semi-solid electrolyte of claim 27 ; and
b. a porous membrane, the semi-solid electrolyte being configured within the three-dimensional matrix.
44. The separator system of claim 43 , wherein the separator system is a battery separator system, a lithium battery separator system, a lithium ion battery separator system, or a lithium sulfur battery separator system.
45. The separator system of claim 43 , wherein the porous membrane is a polymer-ceramic composite or hybrid membrane.
46. The compound of claim 15 , wherein R 1 is heteroalkyl.
47. The compound of claim 15 , wherein R 2 is heteroalkyl.
48. The compound of claim 15 , wherein R 1 and R 2 are heteroalkyl.