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Direct electrochemical extraction of Ti5Si3 from pressed cathode pellets comprising of powdered titanium/silicon-containing metal oxide compounds was investigated by using molten salt electro-deoxidation technology.Three groups of mixtures including TiO2 mixed with SiO2, Ti-bearing blast furnace slag (TBFS) mixed with TiO2, and TBFS mixed with high-titanium slag (HTS) were prepared at the same stoichiometric ratio (Ti∶Si =5∶3) corresponding to the target composition of Ti5Si3, and used as the starting materials in this experiment, respectively.The pressed porous cylindrical pellet of the titanium/silicon-containing compounds served as a cathode, and two different anode systems, i.e.the inert solid oxide oxygen-ion-conducting membrane (SOM)-based anode system and graphite-based anode system were used contrastively.The electrochemical experiment was carried out at 900-1050 ℃ and 3.0-4.0 V in molten CaCl2 electrolyte.The results show that the oxide components were electro-deoxidized effectively and Ti5Si3 could be directly extracted from these complex titanium/silicon-containing metal oxide compounds.