Anisotropic Mg Electrodeposition and Alloying with Ag-based Anodes from Non-Coordinating Mixed-Metal Borohydride Electrolytes for Mg Hybrid Batteries

A highly anisotropic electrodeposition was observed using the hybrid battery electrolyte Mg(BH₄)₂ with LiBH₄ in diglyme. At low overpotentials high aspect ratio platelet morphologies are observed with a strong fiber texture composed of a {10-10} and a {11-20} component, the first evidence of behavior of this kind in magnesium battery electrolytes. At high overpotentials the deposit aspect ratio is indistinguishable but the texture is shown to be primarily composed of a {11-20} fiber texture. The kinetic parameters relative to the relevant crystallographic faces are extracted from electron microscopy images and compared with the observed bulk rate extracted from the electrochemical data. The use of polycrystalline Ag foil substrates with little preferred orientation at the surface allowed highly polycrystalline nucleation at lower overpotentials than that of platinum, likely due to Ag alloying with Mg. Characterization using focused ion beam (FIB) cross-sections with Auger Electron Spectroscopy (AES) elemental analysis confirm that the deposits are primarily Mg although Mg‐Ag alloys of various compositions were observed. It is proposed that the orientation at slow rates of growth is due to the underlying kinetics of adatom diffusion on Mg and that higher rates diminish the phenomenon due to decreased time for adatom diffusion and instead are governed by the rates of adatom formation or more specifically the adatom vacancy formation on the different low-index planes of Mg.