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 Mg2+ 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 MgCl2/AlCl3/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 Mg3Sb2 alloy.

Magnesium based secondary batteries are regarded as a viable alternative to the immensely popular Li‐ion systems. One of the largest challenges is the selection of a Mg anode material since the insertion/extraction processes are kinetically slow because of the large ionic radius and high charge density of Mg2+. In an attempt to bridge the gap between insertion measurements in 3D composite electrode materials and that in an idealized pure model system, we studied the insertion and diffusion of Mg in a thin, massive layer of Sb deposited on Au by using PITT, CV, and potential step experiments. Sb has been suggested as an insertion material because magnesium can form intermetallic compound with it. The layered crystal structure of Sb leads should facilitate formation of such an intermetallic phase. Mg insertion from a MACC/tetraglyme electrolyte into Sb starts 300 mV positive of the onset potential of Mg deposition as shown by cyclic voltammetry. The molar ratio of Mg to Sb agrees well with the stoichiometry of Mg3Sb2 alloy (Zintl‐phase). The diffusion coefficient of Mg‐insertion into Sb – layers and the charge transfer rate have been estimated by the above techniques. Such diffusion coefficients, albeit still somewhat “apparent”, are much more closely related to the true diffusion coefficient in the metal or alloy. The solid‐state diffusion coefficient of Mg into the Sb layers is in the range of 4–8×10−14 cm2 s−1. A very high Tafel slope of 370 mV/dec was found in potential step experiments. Mg insertion was further investigated by XPS measurements. Besides Mg and Sb, Al and Cl signals were also detected, particularly at the outer parts of the layer.

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Magnesium based secondary batteries have been regarded as a viable alternative compared to the immensely popular Li-ion systems owing to its high volumetric capacity. One of the largest challenges is the selection of Mg anode material since the insertion/extraction processes are kinetically slow because the large ionic radius and high charge density of Mg2+ compared with Li+. We prepared very thin films of Sb by electrodeposition on an Au (111) substrate. Monolayer and multilayer deposition (up to 20 Monolayer) were characterized by cyclic voltammetry and STM (Scanning-Tunneling-Microscope). 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 multilayers of Sb the substrate is roughened on the atomic scale due to alloy formation, as demonstrated by CV and STM. Further multilayer deposition correspondingly leads to rough deposit with protrusion of up to 3 nm. The cyclic voltammogram for Mg insertion/de-insertion from MgCl2/AlCl3/Tetraglyme (MACC/TG) electrolyte into/from Sb modified electrode shows a positive shift (400 mV) of the onset potential of Mg deposition compared to that at bare Au electrode. From the charge of Mg deposition, we find that the ratio of Mg to Sb is 1:1; and this somewhat less than expected for the Mg3Sb2 alloy.