Electrolyte compositions and electrochemical double layer capacitors formed there from
The invention generally encompasses phosphonium ionic liquids, salts, compositions and their use in many applications, including but not limited to: as electrolytes in electronic devices such as memory devices including static, permanent and dynamic random access memory, as electrolytes in energy storage devices such as batteries, electrochemical double layer capacitors (EDLCs) or supercapacitors or ultracapacitors, electrolytic capacitors, as electrolytes in dye-sensitized solar cells (DSSCs), as electrolytes in fuel cells, as a heat transfer medium, among other applications. In particular, the invention generally relates to phosphonium ionic liquids, salts, compositions, wherein the compositions exhibit superior combination of thermodynamic stability, low volatility, wide liquidus range, ionic conductivity, and electrochemical stability. The invention further encompasses methods of making such phosphonium ionic liquids, salts, compositions, operational devices and systems comprising the same.
1. An electrochemical double layer capacitor (EDLC) comprising:
a positive electrode;
a negative electrode;
a separator between the positive electrode and the negative electrode; and
an electrolyte composition in contact with the positive electrode, the negative electrode, and the separator, wherein the electrolyte composition comprises:
one or more phosphonium ionic liquids, or one or more phosphonium salts dissolved in a solvent, the one or more phosphonium ionic liquids or phosphonium salts comprising one or more cations of the formula:
P(CH 3 CH 2 CH 2 ) y (CH 3 CH 2 ) x (CH 3 ) 4-x-y (where x,y= 0 to 4 ; x+y≦ 4)
and one or more anions of the formula:
(CF 3 ) x BF 4-x (where x= 0 to 4)
(CF 3 (CF 2 ) n ) x PF 6-x (where n= 0 to 2 ; x= 0 to 4)
(—OCO(CH 2 ) n COO—)(CF 3 ) x BF 2-x (where n= 0 to 2 ; x= 0 to 2)
(—OCO(CH 2 ) n COO—) 2 B (where n= 0 to 2)
(—OSOCH 2 SOO—)(CF 3 ) x BF 2-x (where x= 0 to 2)
(—OCOCOO—) x (CF 3 ) y PF 6-2x-y ( x= 1 to 3 ; y= 0 to 4; 2 x+y≦ 6).
2. The EDLC of claim 1 wherein any one or more of the phosphonium salts may be liquid or solid at a temperature of 100° C. or below.
3. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 CH 2 ) 2 (CH 3 CH 2 )(CH 3 )P + .
4. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P + .
5. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 ) 3 (CH 3 )P + .
6. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 P + .
7. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 ) 4 P + .
8. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 CH 2 ) 3 (CH 3 )P + .
9. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CH 3 CH 2 CH 2 ) 3 (CH 3 CH 2 )P + .
10. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CF 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 P + .
11. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CF 3 CH 2 CH 2 ) 3 (CH 3 CH 2 )P + .
12. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CF 3 CH 2 CH 2 ) 3 (CH 3 )P + .
13. The EDLC of claim 1 wherein the phosphonium based cation is comprised of the formula: (CF 3 CH 2 CH 2 ) 4 P + .
14. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium cations and one or more anions selected from the group consisting of: PF 6 , (CF 3 ) 3 PF 3 , (CF 3 ) 4 PF 2 , (CF 3 CF 2 ) 4 PF 2 , (CF 3 CF 2 CF 2 ) 4 PF 2 , (—OCOCOO—)PF 4 , (—OCOCOO—)(CF 3 ) 3 PF, (—OCOCOO—) 3 P, BF 4 − , CF 3 BF 3 , (CF 3 ) 2 BF 2 , (CF 3 ) 3 BF, (CF 3 ) 4 B, (—OCOCOO—)BF 2 , (—OCOCOO—)BF(CF 3 ), (—OCOCOO—)(CF 3 ) 2 (—OSOCH 2 SOO—)BF 2 , (—OSOCF 2 SOO—)BF 2 , (—OSOCH 2 SOO—)BF(CF 3 ), (—OSOCF 2 SOO—)BF(CF 3 ), (−OSOCH 2 SOO—)B(CF 3 ) 2 , (—OSOCF 2 SOO—)B(CF 3 ) 2 , CF 3 SO 3 , (CF 3 SO 2 ) 2 N, (—OCOCOO—) 2 PF 2 , (CF 3 CF 2 ) 3 PF 3 , (CF 3 CF 2 CF 2 ) 3 PF 3 , (—OCOCOO—) 2 B, (—OCO(CH 2 ) n COO—)BF(CF 3 ), (—OCOCR 2 COO—)BF(CF 3 ), (—OCOCR 2 COO—)B(CF 3 ) 2 , (—OCOCR 2 COO—) 2 B, CF 3 BF(—OOR) 2 , CF 3 B(—OOR) 3 , CF 3 B(—OOR)F 2 , (—OCOCOCOO—)BF(CF 3 ), (—OCOCOCOO—)B(CF 3 ) 2 , (—OCOCOCOO—) 2 B, (—OCOCR 1 R 2 CR 1 R 2 COO—)BF(CF 3 ), and (—OCOCR 1 R 2 CR 1 R 2 COO—)B(CF 3 ) 2 ; and where R, R 1 , and R 2 are each independently H or F.
15. The EDLC of claim 1 wherein the one or more anions are comprised of any one or more of: − O 3 SCF 3 , − O 2 CCF 3 , − O 2 CCF 2 CF 2 CF 3 , CF 3 BF 3 − , C(CN) 3 − , PF 6 − , NO 3 − , − O 3 SCH 3 − , BF 4 − , − O 3 SCF 2 CF 2 CF 3 , − O 2 CCF 2 CF 3 , − O 2 CH, − O 2 CC 6 H 5 , − OCN, CO 3 2− , (—OCOCOO—)BF 2 − , (—OCOCOO—)(CF 3 ) 2 B − , (—OCOCOO—) 2 B − , (CF 3 SO 2 ) 2 N − , (CF 3 ) 2 BF 2 − , (CF 3 ) 3 BF − , CF 3 CF 2 BF 3 − , or − N(CN) 2 .
16. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium salts and one or more of the following solvents: acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoroethylene carbonate (FEC), fluorobenzene (FB), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), phenylethylene carbonate (PhEC), propylmethyl carbonate (PMC), diethoxyethane (DEE), dimethoxyethane (DME), tetrahydrofuran (THF), γ-butyrolactone (GBL), γ-valerolactone (GVL), or mixtures thereof.
17. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium salt and the phosphonium salt is comprised of a cation of the formula: (CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P and an anion of any one or more of the formulas: BF 4 − , PF 6 − , CF 3 BF 3 − , (—OCOCOO—)BF 2 − , (—OCOCOO—)(CF 3 ) 2 B − , (—OCOCOO—) 2 B − , CF 3 SO 3 − , C(CN) 3 − , (CF 3 SO 2 ) 2 N − , or combinations thereof.
18. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium salt and the phosphonium salt is comprised of a cation of the formula: (CH 3 )(CH 3 CH 2 ) 3 P and an anion of any one or more of the formulas: BF 4 − , PF 6 − , CF 3 BF 3 − , (—OCOCOO—)BF 2 − , (—OCOCOO—)(CF 3 ) 2 B − , (—OCOCOO—) 2 B − , CF 3 SO 3 − , C(CN) 3 − , (CF 3 SO 2 ) 2 N − , or combinations thereof.
19. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium salt and the phosphonium salt is comprised of a cation of the formula: (CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 3 P and an anion of any one or more of the formulas: BF 4 − , PF 6 − , CF 3 BF 3 − , (—OCOCOO—)BF 2 − , (—OCOCOO—) 2 B − , (—OCOCOO—)(CF 3 ) 2 B − , CF 3 SO 3 − , C(CN) 3 − , (CF 3 SO 2 ) 2 N − , or combinations thereof.
20. The EDLC of claim 1 wherein the electrolyte composition comprises the phosphonium salt and the phosphonium salt is comprised of a cation of the formula: (CH 3 CH 2 ) 4 P + and an anion of any one or more of the formulas: BF 4 − , PF 6 − , CF 3 BF 3 − , (—OCOCOO—)BF 2 − , (—OCOCOO—)(CF 3 ) 2 B − , (—OCOCOO—) 2 B − , CF 3 SO 3 − , C(CN) 3 − , (CF 3 SO 2 ) 2 N − or combinations thereof.
21. The EDLC of claim 1 wherein the positive electrode active materials and the negative electrode active materials each are selected from the group consisting of carbon blacks, graphite, graphene; carbon-metal composites; polyaniline, polypyrrole, polythiophene; oxides, chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, or selenides of lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium, and combinations thereof.
22. The EDLC of claim 1 wherein the positive electrode active materials and the negative electrode active materials are the same.
23. The EDLC of claim 1 wherein the positive electrode active materials and the negative electrode active materials are different.
24. The EDLC of claim 1 wherein the electrolyte composition further comprises one or more conventional, non-phosphonium salts.
25. The EDLC of claim 24 wherein the phosphonium based ionic liquids or salts and the conventional salts are present in the electrolyte composition at a mole ratio in the range of 1:100 to 1:1, phosphonium based ionic liquid or salt: conventional salt.
26. The EDLC of claim 24 wherein the one or more conventional salts are selected from the group consisting of: tetraethylammonium tetrafluorborate (TEABF 4 ), triethylmethylammonium tetrafluoroborate (TEMABF 4 ), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4 ), 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIIm), and 1-ethyl-3-methylimidazolium hexafluorophosphate (EMIPF 6 ).
27. The EDLC of claim 1 wherein one or more of the hydrogen atoms in the one or more cations or anions are substituted by fluorine.
28. An electrochemical double layer capacitor (EDLC) comprising:
a positive electrode;
a negative electrode;
a separator between the positive electrode and the negative electrode; and
an electrolyte composition in contact with the positive electrode, the negative electrode, and the separator, wherein the electrolyte composition comprises:
a phosphonium salt dissolved in a solvent, where the phosphonium salt is comprised of:
a cation comprised of a 1:3:1 mole ratio of:
(CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 2 (CH 3 )P; and
one or more anions of the formula BF 4 − , PF 6 − , CF 3 BF 3 − , (—OCOCOO—)BF 2 − , (—OCOCOO—)(CF 3 ) 2 B − , (—OCOCOO—) 2 B − , CF 3 SO 3 − , C(CN) 3 − , (CF 3 SO 2 ) 2 N − or combinations thereof.
29. The EDLC of claim 28 wherein the anions are comprised of a mixture of BF 4 — and CF 3 BF 3 — at a concentration of [BF 4 —]:[CF 3 BF 3 —] mole ratio in the range of 100/1 to 1/1.
30. The EDLC of claim 28 wherein the anions are comprised of a mixture of PF 6 — and CF 3 BF 3 — at a concentration of [PF 6 —]:[CF 3 BF 3 —]mole ratio in the range of 100/1 to 1/1.
31. The EDLC of claim 28 wherein the anions are comprised of a mixture of PF6- and BF4- at a concentration of [PF 6 —]:[BF 4 —] mole ratio in the range of 100/1 to 1/1.
32. An electrochemical double layer capacitor (EDLC) comprising:
a positive electrode;
a negative electrode;
a separator between the positive electrode and the negative electrode; and
an electrolyte composition in contact with the positive electrode, the negative electrode, and the separator, wherein the electrolyte composition comprises:
a phosphonium salt dissolved in a solvent, where the phosphonium salt comprises:
a cation comprised of a 1:3:1 mole ratio of:
(CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P
/(CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 2 (CH 3 )P; and
an anion comprised of CF 3 BF 3 − .
33. An electrochemical double layer capacitor (EDLC) comprising:
a positive electrode;
a negative electrode;
a separator between the positive electrode and the negative electrode; and
an electrolyte composition in contact with the positive electrode, the negative electrode,
and the separator, wherein the electrolyte composition comprises:
a phosphonium salt dissolved in a phosphonium solvent, where the salt comprises:
a cation comprised of a 1:3:1 mole ratio of:
(CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 2 (CH 3 )P; and
an anion comprised of BF 4 − .
34. An electrochemical double layer capacitor (EDLC) comprising:
a positive electrode;
a negative electrode;
a separator between the positive electrode and the negative electrode; and
an electrolyte composition in contact with the positive electrode, the negative electrode,
and the separator, wherein the electrolyte composition comprises:
a phosphonium salt dissolved in a solvent, where the phosphonium salt comprises:
a cation comprised of a 1:3:1 mole ratio of:
(CH 3 CH 2 CH 2 )(CH 3 ) 3 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 )(CH 3 ) 2 P/(CH 3 CH 2 CH 2 )(CH 3 CH 2 ) 2 (CH 3 )P; and
an anion comprised of PF 6 − .
35. A hybrid energy storage system comprising an array of EDLCs according to claim 1 and an array of batteries.