Coordination and Thermophysical Properties of Transition Metal Chlorocomplexes in LiCl-KCl Eutectic.

Eutectic LiCl-KCl molten salt is often used in molten salt reactors as the primary coolant due to its high thermal capacity and high solubility of fission products. Thermophysical properties, such as density, heat capacity, and viscosity, are important parameters for engineering applications of molten salts but may be significantly influenced by metal solutes from corrosion of metallic structural materials. The behavior of the LiCl-KCl eutectic composition is well researched, yet the effects on these properties due to chlorocomplex formation from metals dissolved in the salt are less well known. These properties are often difficult to accurately measure from experimental methods due to the issues arising from the dissolved species, such as volatility. Here, we applied a combination of quantum mechanics molecular dynamics (QM-MD) and deep machine learning force field (DP-FF) molecular dynamics simulations to investigate the structural and thermophysical properties of LiCl-KCl eutectic as well as the influence of dissolved transition metal chlorocomplexes NiCl2 and CrCl3 at low concentrations. We find that the dissolution of Ni and Cr in the LiCl-KCl system forms the local tetrahedral (NiCl4)2- and octahedral (CrCl6)3- chlorocomplexes, respectively, which do not have a significant impact on the overall liquid salt structures. In addition, the thermodynamic properties including diffusion constant and specific heat capacity are not significantly affected by these chlorocomplexes. However, the viscosity significantly increases in the temperature range of 673-773 K. This study thus provides essential information for evaluating the effects of dissolved metals on the thermophysical and transport properties of molten salts.