Cathodic Decomposition Electrodes (CDEs) As Standard Reference Electrodes for Molten Salts: Example of the Lithium Eutectic Electrode (LEE) for the LiCl-KCl Eutectic

21 May 2024, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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 (emf) measurements against Li-alloy reference electrodes were used to generate a relationship between the LEE and the standard chlorine electrode (SClE) 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.


Molten Salts
Reference Electrodes


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.