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

Phys Chem Chem Phys. 2008 Apr 7;10(13):1809-18. doi: 10.1039/b719369f. Epub 2008 Feb 12.

Abstract

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 microm) 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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Calcium Chloride / chemistry*
  • Computers
  • Electrochemistry / methods
  • Electrolysis
  • Microscopy, Electron, Scanning
  • Microscopy, Electron, Transmission
  • Models, Chemical
  • Niobium / analysis
  • Niobium / chemistry*
  • Oxides / chemistry*
  • Oxygen / chemistry
  • Potentiometry
  • Powders
  • Software
  • X-Ray Diffraction

Substances

  • Oxides
  • Powders
  • Niobium
  • Calcium Chloride
  • Oxygen