Fluoride ion battery electrolyte compositions
A fluoride ion battery includes a substantially lithium-free anode and cathode. At least one of the anode or cathode contains fluorine, and a substantially lithium-free liquid electrolyte is used for charge transport. The electrolyte is liquid at temperatures below about 200 degrees Celsius, and can be formed from an organic-soluble fluoride salt dissolved in selected classes of solvents.
1. A fluoride ion battery comprising:
an anode and a cathode; where said anode and cathode are lithium-free and comprise different materials; and wherein at least one of the anode and the cathode contains fluorine; and
a lithium-free electrolyte provided between said anode and cathode; said electrolyte comprising an organic-soluble fluoride salt dissolved in a solvent, wherein said organic-soluble fluoride salt comprises a fluorine-substituted or unsubstituted alkylguanidinium cation, phosphazene cation, phosphazenium cation, heterocyclic cation or heterocyclic polymer cation.
2. The fluoride ion battery of claim 1 , wherein said organic-soluble fluoride salt comprises said alkylguanidinium cation.
3. The fluoride ion battery of claim 2 , wherein said alkylguanidinium cation is characterized by the formula: (R 1 R 2 N) 3 C − ; wherein each of R 1 and R 2 is independently a fluorine-substituted or unsubstituted C 1 to C 50 aliphatic group, a C 1 to C 50 cyclic aliphatic group, a C 1 to C 50 fluoroalkyl group, a C 1 to C 50 oligo(ethyleneglycol) group, a C 1 to C 50 alkyl group, or a C 4 to C 50 aryl group; and wherein at least one of R 1 and R 2 is said C 1 to C 50 alkyl group.
4. The fluoride ion battery of claim 3 , wherein each of R 1 and R 2 is independently a C 1 to C 50 aliphatic group or a C 4 to C 50 aryl group.
5. The fluoride ion battery of claim 2 , wherein the organic-soluble fluoride salt is hexamethylguanidinium fluoride.
6. The fluoride ion battery of claim 1 wherein said organic-soluble fluoride salt comprises said phosphazene cation or said phosphazenium cation.
7. The fluoride ion battery of claim 1 , wherein said organic-soluble fluoride salt comprises 1,1,1,3,3,3-hexakis(dimethylamino)diphosphazenium fluoride or tetrakis[tris(dimethylamino)-phosphoranylidenamino]phosphonium fluoride.
8. The fluoride ion battery of claim 1 , wherein said organic-soluble fluoride salt is said heterocyclic cation.
9. The fluoride ion battery of claim 8 , wherein the heterocyclic cation is characterized by the formula X + F − , where X is a heterocyclic ring having between 4 and 7 atoms.
10. The fluoride ion battery of claim 9 , wherein the heterocylic ring of the organic-soluble fluoride salt is an imidazolium, thiazolium, oxazolium, isoxazolium, pyrazolium, pyridinium, piperidinium, pyrrolidinium, pyrilium, pyridazinium, pyrimidinium, pyrazinium, or triazolium.
11. The fluoride ion battery of claim 9 , wherein the heterocyclic ring of the organic-soluble fluoride salt is substituted at one or more positions with a C 1 to C 50 aliphatic group or C 1 to C 50 aryl group.
12. The fluoride ion battery of claim 1 , wherein said organic-soluble fluoride salt is said heterocyclic polymer cation.
13. The fluoride ion battery of claim 1 , wherein the lithium-free electrolyte is a liquid.
14. The fluoride ion battery of claim 13 , wherein the lithium-free electrolyte is said liquid at a temperature greater than −40 degrees Celsius and less than 100 degrees Celsius.
15. The fluoride ion battery of claim 1 , wherein the solvent is a nonaqueous solvent.
16. The fluoride ion battery of claim 1 , wherein the solvent is an organic solvent.
17. The fluoride ion battery of claim 1 , wherein said solvent is selected from the group of acetonitrile, benzonitrile, 4-fluorobenzonitrile, pentafluorobenzonitrile, triethylamine, diisopropylethylamine, 1,2-dimethoxyethane, ethylene carbonate, propylene carbonate, γ-butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propyl methyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, nitromethane, benzene, toluene, chloroform, dichloromethane, 1,2-dichloroethane, dimethylsulfoxide, sulfolane, N,N -dimethylformamide, N,N-dimethylacetamide, carbon disulfide, ethyl acetate, methyl butyrate, n-propyl acetate, methyl propionate, methyl formate, 4-methyl-1,3,-dioxolane, pyridine, methyl isobutyl ketone, methyl ethyl ketone, hexamethylphosphoramide, hexamethylphosphorus triamide, 1-methyl-2-pyrrolidinone, 2-methoxyethyl acetate, sulfones, ethylmethylsulfone, trimethylene sulfone, 1-methyltrimethylene sulfone, ethyl-sec-butyl sulfone, 3,3,3-trifluoropropylmethyl sulfone, 2,2,2-trifluoroethyl sulfone, and a combination thereof.
18. The fluoride ion battery of claim 1 , wherein said anode comprises a material selected from the group consisting of a metal, a metal alloy, a metal oxide, a metal fluoride, an alloy metal fluoride, a metal oxide fluoride, a polyaniline, and a polypyrrole, and wherein said cathode comprises a material selected from the group consisting of a metal, a metal alloy, a metal oxide, a metal fluoride, an alloy metal fluoride, a metal oxide fluoride, a polyaniline, and a polypyrrole.
19. The fluoride ion battery of claim 1 , wherein the cathode comprises fluorine.
20. The fluoride ion battery of claim 1 , wherein the anode comprises fluorine.
21. The fluoride ion battery of claim 1 , wherein said anode comprises Ca, Ce, La, Bi, or Ba.
22. The fluoride ion battery of claim 1 , wherein said cathode comprises BiF 3 , CuF 2 , CoF 3 , SnF 2 , or FeF 3 .
23. The fluoride ion battery of claim 1 , wherein said anode and said cathode are a pair selected from the group consisting of: La/CoF 3 , Ca/CoF 3 , La/CuF 2 , Ca/CuF 2 , and La/BiF 3 .
24. The fluoride ion battery of claim 1 , wherein the fluoride ion battery is rechargeable battery.
25. The fluoride ion battery of claim 1 , wherein the fluoride ion battery is a primary battery.