The Power of Stoichiometry: Conditioning and Speciation of MgCl₂/AlCl₃ in Tetraethylene Glycol Dimethyl Ether-Based Electrolytes

In many Mg-based battery systems, the reversibility of Mg deposition and dissolution is lowered by parasitic formation processes of the electrolyte. Therefore, high Coulombic efficiencies of Mg deposition and dissolution are only achieved after several "conditioning" cycles. As this phenomenon is especially reported for AlCl₃-containing solutions, this study focuses on the "conditioning" mechanisms of MgCl₂/AlCl₃ and MgHMDS₂/AlCl₃ (HMDS = hexamethyldisilazide) in tetraethylene glycol dimethyl ether (TEGDME)-based electrolytes. Electrochemical (cyclic voltammetry) and spectroscopic investigations (²⁷Al nuclear magnetic resonance spectroscopy, Raman spectroscopy, inductively coupled plasma optical emission spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy) reveal that cationic AlCl₂⁺ species in TEGDME-based electrolytes with an AlCl₃/MgCl₂ ratio higher than 1:1 corrode the Mg metal. According to a cementation reaction mechanism, the corrosion of Mg is accompanied with Al deposition. In effect, the consumption of Mg results in low Coulombic efficiencies of Mg deposition and dissolution during the electrolyte "conditioning". After understanding the mechanism of this process, we demonstrate that a careful adjustment of the stoichiometry in MgCl₂/AlCl₃ and MgHMDS₂/AlCl₃ in TEGDME formulations prevents Mg corrosion and results in "conditioning"-free, highly efficient Mg deposition and dissolution.