Cathodic Decomposition Electrodes as Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode for the LiCl-KCl Eutectic

Alternatives to the widely-used standard anodic decomposition reference electrodes in molten salts are necessary to enable more easily reproduced thermochemical and electrochemical data in molten salt electrolytes. The class of standard reference electrodes called cathodic decomposition electrodes (CDEs) are easily constructed and can be used to make thermochemical measurements in molten salts more directly compared to anodic decomposition electrodes. The lithium eutectic electrode (LEE) was chosen as a sample test case for validation and was applied to thermochemical measurements of electroactive species in molten LiCl-KCl eutectic. Transient measurements were made to measure the Li+/Li reduction potential at zero current in pure LiCl-KCl eutectic relative to a Li-alloy reference electrode to validate the reference potential of the LEE. Literature-reported electromotive force measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode and this relationship was used to evaluate measured and reported formal potential measurements for the LiCl-KCl-GdCl3 system. This work demonstrates the general framework for defining CDEs for any molten salt system and a method for calibrating external reference electrodes against a CDE standard reference electrode, improving the ease of obtaining thermochemical and electrochemical measurements in any molten salt system.