There’s actually many “just electrolyze the Oxide” recipes in GT6, which, perhaps can be considered as some sort of placeholders for unfinished production routes? Seldom do IRL metal refining electrolyze the Oxides, with the notable exception of Aluminium. More commonly Chlorides get electrolyzed. For Aluminium, the Chloride is a Molecular Compound instead of an Ionic Compound, and doesn’t conduct electricity even when molten. For ionic chlorides, it’s reasonable to consider it viable for electrolysis.
Also, I agree that at least it should be Electrolysis instead of Centrifugation, for a decomposition of compounds.