Combinations of fluorinated solvents with imide salts or methide salts for electrolytes
Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about −30° C. to about 80° C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO 2 CF 2 CF 3 ) 2 , and LiN(SO 2 CF 3 ) 2 , as well as methide salts, such as LiC(SO 2 CF 3 ) 3 and LiC(SO 2 CF 2 CF 3 ) 3 , may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.
1. An electrolyte for use in an electrochemical cell, the electrolyte comprising:
an electrolyte salt including an imide or methide having at least one fluorinated alkyl group of 1 to 8 carbon atoms; and
a non-fluorinated carboxylic acid ester wherein the non-fluorinated carboxylic acid ester is selected from a group consisting of methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate, and a fluorinated solvent selected from a group consisting of 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane, the fluorinated solvent being over 30% by weight of the electrolyte excluding the electrolyte salt;
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.
2. The electrolyte according to claim 1 , wherein the fluorinated solvent comprises 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.
3. The electrolyte according to claim 1 , wherein the electrolyte salt comprises one of LiC(SO 2 CF 3 ) 3 or LiC(SO 2 CF 2 CF 3 ) 3 .
4. The electrolyte according to claim 1 , wherein the electrolyte salt comprises LiC(SO 2 CF 2 CF 3 ) 3 .
5. The electrolyte according to claim 1 , wherein the fluorinated solvent is between 50% and 75% by weight of the electrolyte excluding the electrolyte salt.
6. The electrolyte according to claim 1 , wherein the electrolyte salt is a first electrolyte salt, wherein the electrolyte further includes a second electrolyte salt different from the first electrolyte salt, and wherein the second electrolyte salt has a lower concentration than the first electrolyte salt.
7. The electrolyte according to claim 6 , wherein the second electrolyte salt has a concentration less than 0.5 M.
8. The electrolyte according to claim 6 , wherein the second electrolyte salt comprises LiPF 6 , LiBF 4 , or a fluoroalkyl-substituted LiPF 6 having a general structure LiPF x R 1-x , where x is from 1 to 5 and at least one R is a fluorinated alkyl group of 1 to 8 carbon atoms, or a fluoroalkyl-substituted LiBF 4 having a general structure LiBF x R 1-x , where x is from 1 to 4 and at least one R is a fluorinated alkyl group of 1 to 8 carbon atoms.
9. The electrolyte according to claim 1 , further comprising a flame-retardant additive at a concentration ranging from about 1% to about 10% by weight of the electrolyte.
10. The electrolyte according to claim 9 , wherein the flame-retardant additive comprises one or more of a phosphate, phosphite, phosphine, and phosphazene.
11. The electrolyte according to claim 9 , wherein the flame-retardant additive comprises P 3 N 3 F x (OR) 6-x such that R is an aryl group or an alkyl group of 1 to 12 carbon atoms, and x is from 1 to 6.
12. The electrolyte according to claim 9 , wherein the flame-retardant additive comprises a cyclic phosphazene.
13. The electrolyte according to claim 1 , further comprising an ionic liquid at 1 to 25% by weight of the electrolyte.
14. The electrolyte according to claim 13 , wherein the ionic liquid comprises one or more of a pyridinium, piperidinium, imidazolium, and phosphonium cations.
15. An electrolyte for use in an electrochemical cell, the electrolyte comprising:
an electrolyte salt including an imide or methide having at least one fluorinated alkyl group of 1 to 8 carbon atoms present at a concentration between 0.6 M and about 2 M;
3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane at 60% to 80% by weight of the electrolyte excluding the electrolyte salt;
ethyl butyrate or ethyl propionate at 10% to 30% by weight excluding the electrolyte salt; and
a cyclic phosphazene at a concentration of 5% to 15% by weight excluding the electrolyte salt,
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.
16. An electrochemical cell comprising:
a positive electrode;
a negative electrode;
an electrolyte providing ionic exchange between the positive electrode and negative electrode and comprising:
an electrolyte salt including an imide or methide having at least one fluorinated alkyl group of 1 to 8 carbon atoms; a non-fluorinated carboxylic acid ester wherein the non-fluorinated carboxylic acid ester is selected from a group consisting of methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate;
and a fluorinated solvent selected from a group consisting of 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane, the fluorinated solvent being over 30% by weight of the electrolyte excluding the electrolyte salt;
wherein the electrolyte is a one-phase solution at a temperature of about −30° C.
17. The electrolyte according to claim 1 , wherein the non-fluorinated carboxylic acid ester is selected from a group consisting of methyl butyrate and ethyl butyrate.
18. The electrolyte according to claim 1 , wherein the fluorinated solvent mixture further includes one or more non-fluorinated cyclic carbonate esters.
19. The electrolyte according to claim 18 wherein the electrolyte includes 10% or less non-fluorinated cyclic carbonate ester by weight, excluding the electrolyte salt.
20. The electrolyte according to claim 18 wherein the electrolyte includes about 7% non-fluorinated cyclic carbonate ester by weight, excluding the electrolyte salt.
21. The electrolyte according to claim 18 wherein the electrolyte includes about 5% non-fluorinated cyclic carbonate ester by weight, excluding the electrolyte salt.
22. The electrolyte according to claim 1 wherein the electrolyte includes substantially no non-fluorinated cyclic carbonate ester.
23. The electrolyte according to claim 1 wherein the fluorinated solvent is 1,1,1,2,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)pentane.