Electrochemical and Thermodynamic Properties of U in LiCl-KCl-UCl₃ salt system

Pyro-processing technology has been considered and examined by several countries as a promising method for the recovery and recycle of uranium and actinide elements from used nuclear fuel. One of the key processes in pyro-processing is an electro-refiner (ER) where the metallic fission products are loaded into an anode basket and dissolved into lithium-potassium chloride (LiCl-KCl) eutectic salt at 773 K. Many researchers have been exploring the fundamental characterizations of U in LiCl-KCl system by using various electrochemical methods, resulting in several reported values of diffusion coefficient, apparent standard potential, and activity coefficient of U in the salt system. In addition, several researchers measured kinetic parameter of U (exchange current density, i₀) by using Tafel and linear polarization (LP) methods. Despite available data sets on this ternary salt system, there are discrepancies due to different experimental conditions, design, size of the cell, and measurement techniques. In addition, the i₀ for U/U³⁺ reaction has only been measured since 2009; therefore, only few data sets are available to date although the i₀ is critical for the development of dynamic ER model. The value of i₀ is a kinetic characteristic in an ideal equilibrium state; therefore, it is very challenging to be measured by experiments. The authors have estimated the values of i₀ via Tafel and linear polarization methods (LP); however, these methods are lack of maintaining electrode surface area during the measurements. In addition, some data are not following the trends from other literature studies due to its difficulties of the measurement. Therefore, further experimental determinations have to be accomplished to understand the i₀ kinetics and the database for the i₀ of U/U³⁺ couple in LiCl-KCl eutectic salt needs to be established systematically. In the present study, an experimental setup was designed and used in a consistent manner to build a meaningful database for U in LiCl-KCl system. LiCl-KCl-UCl₃ salt was prepared at different concentrations and temperatures ranging from 0.5 wt% to 4 wt% and 723 K to 798 K, respectively. Then, CV, open circuit potential (OCP), and electrochemical impedance spectroscopy (EIS) were performed to understand the electrochemical, thermodynamic, and kinetic properties of U. Specially, i₀ values have not been measured via EIS method; therefore, this study provides a good chance to confirm the i₀ values with the new technique