Difference in the Mechanism of Electrochemical Deoxidation of Conducting and Non-conducting Solid Oxide Preforms: An Experimental Demonstration with TiO2 and SiO2 Pellet Electrodes in CaCl2 Melt

摘要

Powder compacted and sintered solid oxide preforms, generally shaped as thin pellets, have been used as the negative electrode of a molten salt electro-deoxidation cell and deoxidation of the electrode is greatly influenced by its electrical conductivity. The deoxidation pattern of electron conducting and non-conducting oxide preforms should, therefore, be different. In order to demonstrate this experimentally, novel electrochemical experiments were carried out with electron conducting TiO2 and non-conducting SiO2 pellet electrodes in calcium chloride melt at 1173 K. The experimental results have shown, as already reported by many previously, that three physically distinct phases, viz. the solid electron conductor, the oxide and the electrolyte melt should coexist for electro-deoxidation of non-conducting SiO2 electrode but only two physically distinct phases, viz. the oxide and the electrolyte melt need only to coexist in the case of conducting TiO2 electrode. It is demonstrated in this study, for the first time, that the 3 Phase Interline (3PI) mechanism, proposed to explain electro-deoxidation of solid oxides in general, stands reduced to 2 Phase Interface (2 PI) mechanism in the case of conducting oxides.