Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors
- Created on Tuesday, 01 November 2011
Low cell resistances are observed when used with modified acetonitrile electrolyte blends.
Double-layer capacitors are unique
energy storage devices, capable of supporting
large current pulses as well as a
very high number of charging and discharging
cycles. The performance of
double-layer capacitors is highly
dependent on the nature of the electrolyte
system used. Many applications,
including for electric and fuel cell vehicles,
back-up diesel generators, wind
generator pitch control back-up power
systems, environmental and structural
distributed sensors, and spacecraft
avionics, can potentially benefit from
the use of double-layer capacitors with
lower equivalent series resistances
(ESRs) over wider temperature limits.
Higher ESRs result in decreased power
output, which is a particular problem at
lower temperatures. Commercially available
cells are typically rated for operation
down to only –40 °C.
Previous briefs [for example, “Low Temperature Supercapacitors” (NPO- 44386), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), p. 32, and “Supercapacitor Electrolyte Solvents With Liquid Range Below –80 °C” (NPO-44855), NASA Tech Briefs, Vol. 34, No. 1 (January 2010), p. 44] discussed the use of electrolytes that employed low-melting-point co-solvents to depress the freezing point of traditional acetonitrile-based electrolytes. Using these modified electrolyte formulations can extend the lowtemperature operational limit of double- layer capacitors beyond that of commercially available cells. This previous work has shown that although the measured capacitance is relatively insensitive to temperature, the ESR can rise rapidly at low temperatures, due to decreased electrolyte conductance within the pores of the high-surface-area carbon electrodes. Most of these advanced electrolyte systems featured tetraethylammonium tetrafluoroborate (TEATFB) as the salt. More recent work at JPL indicates the use of the asymmetric quaternary ammonium salt triethylmethylammonium tetrafluoroborate (TEMATFB) or spiro-(l,l’)-bipyrrolidium tetrafluoroborate (SBPBF4) in a 1:1 by volume solvent mixture of acetonitrile (AN) and methyl formate (MF) enables double- layer capacitor cells to operate well below –40 °C with a relatively low ESR. Typically, a less than two-fold increase in ESR is observed at –65 °C relative to room-temperature values, when these modified electrolyte blends are used in prototype cells. Double-layer capacitor coin cells filled with these electrolytes have displayed the lowest measured ESR for an organic electrolyte to date at low temperature (based on a wide range of electrolyte screening studies at JPL). The cells featured high-surface-area (≈2,500 m/g) carbon electrodes that were 0.50 mm thick and 1.6 cm in diameter, and coated with a thin layer of platinum to reduce cell resistance. A polyethylene separator was used to electrically isolate the electrodes.
This work was done by Erik J. Brandon,
Marshall C. Smart, and William C. West of
Caltech for NASA’s Jet Propulsion Laboratory.
In accordance with Public Law 96-517, the contractor has elected to retain title to this invention. Inquiries concerning rights for its commercial use should be addressed to:
• Innovative Technology Assets Management JPL
• Mail Stop 202-233
• 4800 Oak Grove Drive
• Pasadena, CA 91109-8099
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