Additives for reducing ESR gain in electrochemical double layer capacitors
The present disclosure relates to electric double layer capacitors (EDLCs) that include an alkylating or arylating agent additive capable of scavenging nucleophilic species generated during operation of the EDLC. The additives for the electric double layer capacitors (EDLCs) including an alkylating or arylating agent are described herein. The alkylating or arylating reagent comprises a compound of the formula I: R—X (I) wherein R and X are described herein.
1. An electrochemical double-layer capacitor, comprising:
a cathode;
an anode;
a separator;
an electrolyte; and
an additive comprising a compound of formula I:
R—X
wherein:
R is saturated alkyl, unsaturated alkyl, saturated branched alkyl, aryl, substituted aryl or substituted alkyl;
X is I, Br, Cl, —SO 2 F, —SO 2 CF 3 , —OCH 3 , —N(SO 2 F) 2 , —N(SO 2 CF 3 ) 2 , —N(CN) 2 , —Si(CH 3 ) 3 , —O—S(O) 2 —OCH 3 , —S(O) 2 —O—CF 3 , or tosylate, wherein
a concentration of the compound of formula I in the electrolyte of the electrochemical double-layer capacitor is selected from the group consisting of about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, and 9% vol %.
2. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is an alkyl chloride.
3. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is an aryl chloride.
4. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is at least one of chlorobenzene, 1-chloro-n-butane, bromobenzene, 1-bromo-n-butane, 1-chloropropane, and 1-bromopropane.
5. The electrochemical double-layer capacitor of claim 4 , wherein the compound of formula I is chlorobenzene.
6. The electrochemical double-layer capacitor of claim 4 , wherein the compound of formula I is 1-chloro-n-butane.
7. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is included in the electrolyte, the electrolyte comprising an ionic species and a solvent.
8. The electrochemical double-layer capacitor of claim 7 , wherein the solvent is at least one of acetonitrile, propionitrile, and butyronitrile.
9. The electrochemical double-layer capacitor of claim 7 , wherein the solvent is at least one of gamma-butyrolactone, propylene carbonate, ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
10. The electrochemical double-layer capacitor of claim 7 , wherein the ionic species is a quaternary ammonium salt.
11. The electrochemical double-layer capacitor of claim 10 , wherein the quaternary ammonium salt is at least one of spiro-bipyrrolidinium tetrafluoroborate (SBP BF 4 ), tetraethyl ammonium tetrafluoroborate (TEA TFB), and triethyl(methyl)ammonium tetrafluoroborate.
12. The electrochemical double-layer capacitor of claim 7 , wherein the electrolyte further comprises a stabilizer.
13. The electrochemical double-layer capacitor of claim 12 , wherein the stabilizer is benzonitrile.
14. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is included in the separator.
15. The electrochemical double-layer capacitor of claim 1 , wherein the compound of formula I is included in at least one of the anode and the cathode.
16. The electrochemical double-layer capacitor of claim 15 , wherein the compound of formula I is included in a binder of at least one of the cathode, and the anode.
17. The electrochemical double-layer capacitor of claim 1 , having an operating voltage of greater than about 2.7 V.
18. The electrochemical double-layer capacitor of claim 1 , having a rated maximum temperature of greater than about 50° C.
19. An electrochemical double-layer capacitor, comprising:
a cathode;
an anode;
a separator;
an electrolyte;
a stabilizer; wherein the stabilizer is benzonitrile; and
an additive comprising a compound of formula I:
R—X (I)
wherein:
R is saturated alkyl, unsaturated alkyl, saturated branched alkyl, aryl, substituted aryl or substituted alkyl;
X is I, Br, Cl, FSO 2 , CF 3 SO 2 , OCH 3 , N(SO 2 F) 2 , N(SO 2 CF 3 ) 2 , N(CN) 2 , Si(CH 3 ) 3 , SO 4 CH 3 , CF 3 SO 3 , or tosylate, wherein
a total concentration of the compound of formula I and the stabilizer in the electrolyte of the electrochemical double-layer capacitor is less than or equal to about 10% by volume.
20. The electrochemical double-layer capacitor of claim 19 , wherein the total concentrations of the compound of formula I and the stabilizer is about the same.
21. The electrochemical double-layer capacitor of claim 19 wherein the total concentrations of the compound of formula I and the stabilizer is about 5%.
22. The electrochemical double-layer capacitor of claim 19 , wherein the compound of formula I is chlorobenzene.
23. The electrochemical double-layer capacitor of claim 19 , wherein the compound of formula I is 1-chloro-n-butane.
24. A method of manufacturing an EDLC cell, the method comprising:
disposing a cathode on a positive current collector;
disposing an anode on a negative current collector;
disposing a separator between the positive current collector and the negative current collector to form the EDLC cell;
disposing the EDLC cell in a container; and
infiltrating the EDLC cell with an electrolyte formulation comprising: an ionic species, a solvent, and an additive comprising a compound of formula I:
R—X
wherein:
R is saturated alkyl, unsaturated alkyl, unsaturated branched alkyl, aryl, substituted aryl, or substituted alkyl;
X is I, Br, Cl, FSO 2 , CF 3 SO 2 , OCH 3 , N(SO 2 F) 2 , N(SO 2 CF 3 ) 2 , N(CN) 2 , Si(CH 3 ) 3 , SO 4 CH 3 , CF 3 SO 3 , or tosylate, and
a concentration of the compound of formula I in the electrolyte selected from the group consisting of about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, and 9% vol %.
25. The method of claim 24 , wherein the electrolyte further comprises a stabilizer.
26. The method of claim 25 , wherein the stabilizer is benzonitrile.
27. The method of claim 24 , wherein the compound of formula I is formulated to alkylate or arylate tertiary amines present within the EDLC cell.
28. The method of claim 24 , wherein the compound of formula I is an alkyl chloride.
29. The method of claim 24 , wherein the compound of formula I is an aryl chloride.
30. The method of claim 24 , wherein the compound of formula I includes at least one of chlorobenzene, 1-chloro-n-butane, bromobenzene, 1-bromo-n-butane, 1-chloropropane, and 1-bromopropane.
31. The method of claim 30 , wherein the compound of formula I is chlorobenzene.
32. The method of claim 24 , wherein the solvent includes at least one of acetonitrile, propionitrile, and butyronitrile.
33. The method of claim 24 , wherein the ionic species is at least one of spiro-bipyrrolidinium tetrafluoroborate (SBP BF 4 ), tetraethylammonium tetrafluoroborate (TEA TFB), and triethyl(methyl)ammonium tetrafluoroborate.
34. The method of claim 24 , wherein the EDLC cell has an operating voltage of greater than about 2.7 volts.
35. The method of claim 24 , wherein the EDLC cell has an operating temperature of greater than about 50 degrees Celsius.