The Cathode Process of Aluminum Chloride Electrolysis

"The cathodic kinetics of aluminum deposition from aluminum chloridealkali chloride melts was studied by use of electro-cnemical transient techniques at 700 °C. Aluminum deposited as an insoluble product on a glassy carbon electrode and as a partly soluble product on a tungsten electrode. The deposition was found to be a simple diffusion controlled process involving the exchange of three electrons. The diffusion coefficient of aluminum chloride was calculated - 4.sx10-s cm2 ·S-I in AlCl3 -NaCl-LiCl melts and 2.6x10-s cm2 ·S-' in AlCl3 -NaCl-KCl melts. For AlCl3 -NaCl-CsCl system the diffusion coefficient exhibited some uncertainty due to nucleation. The determined rate constant of aluminum deposition reaction was on the order of 10-' -10-2 cm'S:' Constant potential electrolysis was carried out. TiB2 was well wetted by aluminum. The species of melts penetrated into graphite and glassy carbon but not into tungsten. The diffusion coefficient of species in glassy carbon was evaluated.IntroductionAluminum chloride electrolysis is attractive for its power saving of 30%. Different process to circumvent the conventional chlorization to obtain aluminum chloride economically, such as directly chlorizating mixture of Al~03 and C in a cell with A-shaped laminated bipolar electrodes by rising chlorine (1), or by use of a composite anode (2), will promote the electrolysis technology to be realized industrially. With the appearance of the Alcoa process periodically there are studies on the kinetics of aluminum deposition. Some discrepancies seem to exist on the mechanism of aluminum deposition. Borne studies (3,4,5) showed that the deposition of aluminum was hindered by diffusion process in the melts. M.Gabco et a1. (6) claimed a preceding dissociation of a complex being the rate controlled step. This paper presents our results on the mechanism of aluminum deposition from the study by use of transient techniques and some results from constant potential electrolysis."