Electrochemical Study of Nd and Pr Co-Deposition onto Mo and W from Molten Oxyfluorides

Electrodeposition processes of neodymium and praseodymium in molten NdF3 + PrF3 + LiF + 1 wt.%Pr6O11 + 1 wt.%Nd2O3 and NdF3 + PrF3 + LiF + 2 wt.%Pr6O11 + 2 wt.%Nd2O3 electrolytes at 1323 K were investigated. Cyclic voltammetry, square wave voltammetry, and open circuit potentiometry were applied to study the electrochemical reduction of Nd(III) and Pr(III) ions on Mo and W cathodes. It was established that a critical condition for Nd and Pr co-deposition in oxyfluoride electrolytes was a constant praseodymium deposition overpotential of ≈−0.100 V, which was shown to result in co-deposition current densities approaching 6 mAcm−2. Analysis of the results obtained by applied electrochemical techniques showed that praseodymium deposition proceeds as a one-step process involving exchange of three electrons (Pr(III)→Pr(0)) and that neodymium deposition is a two-step process: the first involves one electron exchange (Nd(III)→Nd(II)), and the second involves an exchange of two electrons (Nd(II)→Nd(0)). X-ray diffraction analyses confirmed the formation of metallic Nd and Pr on the working substrate. Keeping the anodic potential to the glassy carbon working anode low results in very low levels of carbon oxides, fluorine and fluorocarbon gas emissions, which should qualify the studied system as an environmentally friendly option for rare earth metal deposition. The newly reported data for Nd and Pr metals co-deposition provide valuable information for the recycling of neodymium-iron-boron magnets.