Electrochemical behavior and electrodeposition of dysprosium in ionic liquids based on phosphonium cations

Abstract

The electrochemical behavior and the electrodeposition of dysprosium (Dy) in phosphonium-cation-based ionic liquid were investigated in this study. A new group of the room-temperature ionic liquids (RTILs) based on phosphonium cations with bis(trifluoromethylsulfonyl)amide anions was applied as novel electrolytic solutions. The cyclic voltammetric measurements resulted in one step reduction of the trivalent dysprosium ion in phosphonium-cation-based ionic liquid. On the other hand, no anodic peak ascribed to the oxidation of dysprosium metal was observed in this electroanalytical study. The diffusion coefficient and the activation energy for diffusion of the trivalent Dy complex in IL were estimated using semi-integral analysis, because it is important to analyze the diffusion properties to recover Dy through electrowinning methods. The diffusion coefficient of Dy(III) which was calculated to be 2.0 × 10⁻¹² m² s⁻¹ at 25 °C, closed to that of the trivalent lanthanoid ion such as Eu(III) and Sm(III) in phosphonium-cation-based ionic liquid. In addition, the activation energy for diffusion was estimated to be 65 kJ mol⁻¹ (0.5 M) and 49 kJ mol⁻¹ (0.075 M). The estimated activation energy for diffusion was affected by the concentration of the electrolytic solution, since the RTILs had relatively strong electrostatic interactions between the metal cations and the solvent anions. Furthermore, the electrodeposition of Dy in phosphonium-cation-based IL was carried out using a two-electrode system constructed with a copper plate cathode and dysprosium metal anode. Energy dispersive X-ray analysis of electrodeposits showed a sharply peaked spectrum corresponding to the characteristic X-ray lines of Dy. In addition, the obtained Dy, with the exception of the surface layer, was confirmed to be in the metallic electronic state by X-ray photoelectron spectroscopy.