The use of room temperature ionic liquids (RTILs) for electrochemical applications such as fuel cells, batteries, dye-sensitized solar cells, and supercapacitors, has gained significant interest over the last decade. Despite the increase in attention, a universal reference electrode for use in RTIL electrochemistry has not been adopted. A stable, easy to prepare, and reproducible reference electrode, analogous to Ag/AgCl reference electrodes for aqueous electrochemistry, is crucial for accurately determining redox potentials as well as for comparing these potentials between RTILs and between research labs.

Electrochemical work in RTILs often rely on quasi-reference electrodes (QREs),¹ such as Ag or Pt wire, which must be calibrated by the addition of a redox couple (e.g. ferrocene/ferrocenium) after each electrochemical measurement. These quasi-reference electrodes are difficult to reproduce, likely due to the quality of the wire used and the presence of surface adsorbates. Furthermore, they have been known to exhibit potential drift during use, with 10s to 100s of mV drift often observed. Ferrocene is added after the experiment, however this one-point calibration of the QRE does not necessarily apply throughout the entire experiment, as the QRE may drift during the measurement.²

We report on reference electrodes designed for use in ionic liquids, which exhibit stable potential over several months of experimental use. One successful example is based on a silver wire coated with silver sulfide.³ The reference electrode potential is determined by the concentrations of Ag⁺ and S²⁻, which are established by the solubility of the Ag₂S coating on the Ag wire. Our reference electrode can be prepared and used in a normal air atmosphere, and does not need to be assembled and used in a glovebox, or protected from light. The reference electrode has been characterized by voltammetry measurements of ferrocene and cobaltocenium hexafluorophosphate, and was found to slowly drift to more positive potentials at a rate of <1 mV/day for five RTILs investigated over the course of 2+ months.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. IM release LLNL-ABS-748348.

(1) Electrochemical aspects of ionic liquids, 2nd ed.; Ohno, H., Ed.; John Wiley & Sons Inc., 2011.

(2) Torriero, A. A. J.; Sunarso, J.; Howlett, P. C. Electrochim. Acta 2012, 82, 60–68.

(3) Horwood, C.; Stadermann, M. Electrochem. Commun. 2018, 88 (December 2017), 105–108.