Modified ionic liquids containing bicyclophosphate moiety
A bicyclophosphate-modified ionic liquid compound, the synthesis thereof, an electrochemical electrolyte containing a bicyclophosphate-modified ionic liquid compound, and energy storage device containing the electrolyte are disclosed.
1. An electrical energy storage device electrolyte comprising:
a) an aprotic organic solvent system;
b) a metal salt; and
c) an ionic liquid compound comprising:
an anion (A − ); and
a cation attached to a bicyclophosphate moiety according to the formula:
wherein:
CAT + is a pyrrolidinium, piperdinium, azepanium, sulfonium, phosphonium, pyridine, imidazolium or a 5- or 6-membered heterocyclic ring having 1 to 3 heteroatoms as ring members including nitrogen, oxygen, silicon or sulfur; and
L is (a) a linker, including a C 1 -C 8 alkyl, alkenyl, alkynyl, alkoxy, ester, carbonyl, phenyl, thioether, sulfoxide, azo or aryl group, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide; (b) O, S, NH, or C; or (c) O, S, NH, or C attached to the linker, with the proviso that when L is an ester group then CAT+ is not an imidazolium.
2. The electrolyte of claim 1 , wherein the anion comprises a halide, nitrate, phosphate, imide, borate, aluminate, arsenide, cyanide, thiocyanate, nitrite, benzoate, carbonate, chlorate, chlorite, chromate, sulfate, sulfite, silicate, thiosulfate, chalcogenide, pnictogenide, crystallogenide, oxalate, acetate, formate or hydroxide.
3. The electrolyte of claim 2 , wherein the anion comprises Cl, Br, NO 3 , PF 6 , TFOP, TFSI, BETI, BOB or BF 4 .
4. The electrolyte of claim 1 , wherein the aprotic organic solvent comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphate, phosphite mono- or polyphosphazene or mixtures thereof.
5. The electrolyte of claim 1 , wherein the cation of the metal salt is an alkali metal.
6. The electrolyte of claim 5 , wherein the alkali metal is lithium or sodium.
7. The electrolyte of claim 1 , wherein the cation of the metal salt is aluminum or magnesium.
8. The electrolyte of claim 1 , further comprising at least one additive.
9. The electrolyte of claim 8 , wherein the at least one additive comprises sulfur-containing compounds, phosphorus-containing compounds, boron-containing compounds, silicon-containing compounds, fluorine-containing compounds, nitrogen-containing compounds, compounds containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydrides or the mixtures thereof.
10. The electrolyte of claim 8 , wherein the at least one additive is present in a concentration of from 0.01 wt. % to 10 wt. % in the electrolyte.
11. An ionic liquid compound comprising:
an anion (A − ); and
a cation attached to a bicyclophosphate moiety according to the formula:
wherein:
CAT + is a pyrrolidinium, piperdinium, azepanium, sulfonium, phosphonium, pyridine, imidazolium or a 5- or 6-membered heterocyclic ring having 1 to 3 heteroatoms as ring members including nitrogen, oxygen, silicon or sulfur; and
L is (a) a linker, including a C 1 -C 8 alkyl, alkenyl, alkynyl, alkoxy, ester, carbonyl, phenyl, thioether, sulfoxide, azo or aryl group, wherein any of the carbon or hydrogen atoms therein are optionally further substituted with a halide; (b) O, S, NH, or C; or (c) O, S, NH, or C attached to the linker, with the proviso that when L is an ester group then CAT+ is not an imidazolium.
12. The compound of claim 11 , wherein the anion comprises a halide, nitrate, phosphate, imide, borate, aluminate, arsenide, cyanide, thiocyanate, nitrite, benzoate, carbonate, chlorate, chlorite, chromate, sulfate, sulfite, silicate, thiosulfate, chalcogenide, pnictogenide, crystallogenide, oxalate, acetate, formate or hydroxide.
13. The compound of claim 11 , wherein the anion comprises Cl, Br, NO 3 , PF 6 , TFOP, TFSI, BETI, BOB or BF 4 .
14. An electrochemical energy storage device comprising:
a cathode;
an anode;
an electrolyte according to claim 1 ; and
a separator.
15. The device of claim 14 , wherein the cathode comprises a lithium metal oxide, spinel, olivine, carbon-coated olivine, vanadium oxide, lithium peroxide, sulfur, polysulfide, a lithium carbon monofluoride or mixture thereof.
16. The device of claim 15 , wherein the lithium metal oxide is LiCoO 2 , LiNiO 2 , LiNi x Co y Met z O 2 , LiMn 0.5 Ni 0.5 O 2 , LiMn 0.1 Co 0.1 Ni 0.8 O 2 , LiMn 0.2 Co 0.2 Ni 0.6 O 2 , LiMn 0.3 Co 0.2 Ni 0.5 O 2 , LiMn 0.33 Co 0.33 Ni 0.33 O 2 , LiMn 2 O 4 , LiFeO 2 , Li 1+x′ Ni α Mn μ Co γ Met′ δ O 2-z′ F z′ , or A n′ B 2 (XO 4 ) 3 , wherein Met is Al, Mg, Ti, B, Ga, Si, Mn or Co; Met′ is Mg, Zn, Al, Ga, B, Zr or Ti; A is Li, Ag, Cu, Na, Mn, Fe, Co, Ni, Cu or Zn; B is Ti, V, Cr, Fe or Zr; X is P, S, Si, W or Mo; and wherein 0≤x≤0.3, 0≤y≤0.5, 0≤z≤0.5, 0≤x′≤0.4, 0≤α≤1, 0≤β≤1, 0≤γ≤1, 0≤δ≤0.4, 0≤z′≤0.4 and 0≤h′≤3.
17. The device of claim 14 , wherein the anode comprises lithium metal, graphitic material, amorphous carbon, Li 4 Ti 5 O 12 , tin alloy, silicon, silicon alloy, intermetallic compound, or mixture thereof.
18. The device of claim 14 , wherein the device comprises a lithium battery, lithium-ion battery, lithium-sulfur battery, lithium-air battery, sodium ion battery, magnesium battery, lithium/MnO 2 battery, or Li/poly(carbon monofluoride) battery.
19. The device of claim 14 , wherein the device comprises a capacitor or solar cell.
20. The device of claim 14 , wherein the device comprises an electrochemical cell.
21. The device of claim 14 , wherein the separator comprises a porous separator separating the anode and cathode from each other.
22. The device of claim 21 , wherein the porous separator comprises an electron beam-treated micro-porous polyolefin separator or a microporous polymer film comprising nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, or co-polymer or blend of any two or more such polymers.
23. The device of claim 14 , wherein the aprotic organic solvent system comprises an open-chain or cyclic carbonate, carboxylic acid ester, nitrite, ether, sulfone, ketone, lactone, dioxolane, glyme, crown ether, siloxane, phosphoric acid ester, phosphite, mono- or polyphosphazene or mixture thereof.
24. The device of claim 14 , wherein the aprotic organic solvent system is present in a concentration of from 60 wt. % to 90 wt. % in the electrolyte.
25. The device of claim 14 , wherein the cation of the metal salt is an alkali metal.
26. The device of claim 25 , wherein the alkali metal is lithium or sodium.
27. The device of claim 14 , wherein the cation of the metal salt is aluminum or magnesium.
28. The device of claim 14 , wherein the metal salt is present in a concentration of from 10 wt. % to 30 wt. % in the electrolyte.
29. The device of claim 14 , wherein the electrolyte further comprises at least one additive.
30. The device of claim 29 , wherein the at least one additive comprises a sulfur-containing compound, phosphorus-containing compound, boron-containing compound, silicon-containing compound, fluorine-containing compound, nitrogen-containing compound, compound containing at least one unsaturated carbon-carbon bond, carboxylic acid anhydride, epoxide, or mixture thereof.
31. The device of claim 29 , wherein the at least one additive is present in a concentration of from 0.01 wt. % to 10 wt. % in the electrolyte.