Thermodynamic description of molten salt systems: KCl-LiCl-NaCl and KCl-LiCl-NdCl3

The mixture of KCl and LiCl has been used as electrolyte in the electrorefining process to recover uranium from used nuclear fuels due to the low melting point. However, lanthanides and sodium in the reactor waste continuously dissolve into it and thus alter its thermodynamic properties. To understand the thermodynamic behavior evolution of the electrolyte with the accumulation of impurities, thermodynamic modeling for KCl-LiClNaCl and KCl-LiCl-NdCl3 and four constituent binary systems in the entire composition space was performed using the CALPHAD (CALculation of PHAse Diagrams) approach. The ionic liquid was described by the twosublattice model, where neutral species were introduced to consider short-range ordering (SRO) within the melt, whereas the solid solution was modeled based on the Compound Energy Formalism. Literature data on phase equilibria and thermochemical properties were critically evaluated and used during the optimization of thermodynamic parameters for KCl-LiCl-NaCl and KCl-LiCl-NdCl3 and their subsystems. The calculated phase diagrams and mixing enthalpies are in good agreement with the experimental data. The thermodynamic modeling for the KCl-LiCl-NdCl3 system was carried out for the first time. To fill the gap in experimental measurement, enthalpy of mixing for the KCl-LiCl-NdCl3 melt was estimated using the surrounded-ion model. These data then served as critical inputs for thermodynamic optimization. The present study can provide insights into thermodynamic property evolution of the electrolyte and solubility limit of various impurities during the electrorefining process.

Automated summary

Thermodynamic modeling and optimization were conducted to investigate the thermodynamic behavior evolution of KCl-LiClNaCl and KCl-LiCl-NdCl3 systems, as well as their constituent binary systems. The study provides insights into the thermodynamic properties of the electrolyte and the variation of solubility limits of different impurities during the electrorefining process.