(Invited) Thermodynamic Properties of Rare-Earth Alloys Relevant for Efficient Rare-Earth Recovery in Molten Salts

Abstract

Electrode materials of Fe, liquid Bi, and Sn were investigated to enhance the electrochemical recovery of rare-earth elements in molten salts (eutectic LiCl-KCl) at 500‒700 °C, leveraging their chemical interactions with rare-earth elements. Using Nd as a prototypical example, the degree of interactions was quantified based on electromotive force (emf) measurements of Nd alloys (Nd-Fe, Nd-Bi, and Nd-Sn). Temperature-dependent emf values of the Nd alloys were used to determine the thermodynamic properties such as the partial molar Gibbs energy (chemical potential), entropy, and enthalpy of Nd. In addition, the phase behavior of Nd alloys was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) to determine transition temperatures and microstructures of Nd alloy electrodes. Based on these fundamental properties of Nd alloys, the Nd-Sn alloy at mole fraction, x Nd = 0.10 was selected as the reference electrode and employed for electrochemical measurements in three-electrode cells in molten chloride salt (LiCl-KCl-NdCl3). The stability of Nd-Sn reference electrode was maintained less than 1 mV deviation between identical constructs during entire measurements, originating from the two phase (liquid + NdSn3) stability of the binary Nd-Sn alloy at 500‒700 °C. Finally, electrodeposition of Nd onto these interacting electrode materials was conducted to assess the recovery efficiency of Nd from molten chloride salt.