Electrochemistry of Neodymium in an Equimolar NaCl-KCl Melt without and with Addition of Fluoride Ions

Abstract

The paper presents the results of neodymium electrochemical behavior in chloride and chloride-fluoride melts. It was shown that the process of neodymium electroreduction in the NaCl-KCl-NdCl3 melt proceeds in two stages. By diagnostic criteria of voltammetry it was established that the discharge process of Nd(III) to Nd(II) at a sweep rate in the range of 0.6 ≤  ≤ 1.0 V s-1 is not complicated by disproportionation reaction. In this study diffusion coefficients, activation energy of diffusion for Nd(III) chloride complexes and standard rate constants of charge transfer for the Nd(III)/Nd(II) redox couple in the NaCl-KCl melt were determined. The nature of the working electrode on the standard rate constants of charge transfer for the Nd(III)/Nd(II) redox couple has been studied by cyclic voltammetry and electrochemical impedance spectroscopy. The formal redox potentials E*Nd(III)/Nd(II) in the NaCl-KCl melt were obtained from the cyclic voltammetry data. It was shown that the addition of fluorine anions into the NaCl-KCl-NdCl3 melt leads to stabilization of the higher oxidation state of neodymium in chloride-fluoride melts and the intermediate oxidation state Nd(II) does not exist in these melts.

Electrolysis in Chloride Molten Salts for Sustainable Critical Metals Production and Recovery

“…Recent developments in the use of electrolyte additives are noteworthy in this context. 8 Additives can enable more compact and thus ultra-high-purity electrowon metal that circumvents the need for postpurification, thereby maintaining the energy requirements at a minimal value during metalmaking.…”