Passivation of the aluminium cathode during deposition of aluminium from aluminium chloride-sodium chloride melts

The kinetics of aluminium deposition from NaCl-AlCl₃ melts (c_AlCl3 < 10 mol%) contained in alumina crucibles was studied by linear sweep voltammetry and potential step amperometry at temperatures around 820°C. At low concentrations (c_AlCl3 < 0.4 mol%) the reduction of AlCl₃ on liquid aluminium has been found to be diffusion controlled. At higher concentrations a passivation of the aluminium electrode was observed during the deposition reaction. The passivation appears to be caused by precipitation of alumina from supersaturated melt in the diffusion layer at the aluminium cathode.