Antimony deposition onto Au(111) and insertion of Mg

Magnesium-based secondary batteries have been regarded as a viable alternative to the immensely popular Li-ion systems owing to their high volumetric capacity. One of the largest challenges is the selection of Mg anode material since the insertion/extraction processes are kinetically slow because of the large ionic radius and high charge density of Mg(2+) compared with Li(+). In this work, we prepared very thin films of Sb by electrodeposition on a Au(111) substrate. Monolayer and multilayer deposition (up to 20 monolayers) were characterized by cyclic voltammetry (CV) and scanning tunneling microscopy (STM). Monolayer deposition results in a characteristic row structure; the monolayer is commensurate in one dimension, but not in the other. The row structure is to some extent maintained after deposition of further layers. After dissolution of the Sb multilayers the substrate is roughened on the atomic scale due to alloy formation, as demonstrated by CV and STM. Further multilayer deposition correspondingly leads to a rough deposit with protrusions of up to 3 nm. The cyclic voltammogram for Mg insertion/de-insertion from MgCl(2)/AlCl(3)/tetraglyme (MACC/TG) electrolyte into/from a Sb-modified electrode shows a positive shift (400 mV) of the onset potential of Mg deposition compared to that of a bare Au electrode. From the charge of the Mg deposition, we find that the ratio of Mg to Sb is 1:1, which is somewhat less than expected for the Mg(3)Sb(2) alloy.