Computer-aided control of electrolysis of solid Nb₂O₅ in molten CaCl₂

Low energy production of Nb powders via computer-aided control (CAC) of two-electrode electrolysis of porous Nb₂O₅ pellets (ca. 1.0 g) has been successfully demonstrated in molten CaCl₂ at 1123 K. It was observed that potentiostatic electrolysis of the oxide in a three-electrode cell led to a cell voltage, i.e. the potential difference between the working (cathode) and counter (anode) electrodes, that decreased to a low and stable value within 1–2 h of the potential application until the end of the electrolysis (up to 12 h in this work). The cell voltage varied closely according to the current change. The stabilised cell voltage was below 2.5 V when the cathode potential was more positive than that for the reduction of Ca²⁺, leading to much lower energy consumption than that of constant voltage (>3.0 V) two-electrode electrolysis, as previously reported. Using a computer to program the variation of the cell voltage of two-electrode electrolysis according to that observed in the potentiostatic three-electrode electrolysis (0.05 V vs. Ca/Ca²⁺), a Nb powder with ca. 3900 ppm oxygen was produced in 12 h, with the energy consumption being 37.4% less than that of constant voltage two-electrode electrolysis at 3.0 V. Transmission electron microscopy revealed thin oxide layers (4–6 nm) on individual nodular particles (1–5 µm) of the obtained Nb powder. The oxide layer was likely formed in post-electrolysis processing operations, including washing in water, and contributed largely to the oxygen content in the obtained Nb powder.