Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Magnesium batteries are currently attracting a lot of interest as a next generation battery technology. One critical issue is to find a suitable electrolyte and herein we explore an electrolyte based on magnesocene (MgCp<jats:sub>2</jats:sub>) in tetrahydrofuran (THF), aiming for low‐voltage Mg batteries, with respect to: Mg plating characteristics, electrochemical stability windows, electrolyte speciation, and electrolyte decomposition reactions; both experimentally and computationally. Overall, the electrolyte does not seem to decompose on a Mg metal anode and most likely reduced solvation of Mg<jats:sup>2+</jats:sup> by the Cp<jats:sup>−</jats:sup> anion is important and species such as MgCp<jats:sub>2</jats:sub>THF<jats:sub>2</jats:sub> may play an important role for Mg plating with small overpotential. The oxidation limit is largely determined by the Cp<jats:sup>−</jats:sup> anion and density functional theory predicted oxidation reactions point to polymerized end‐products to be possible. Furthermore, <jats:italic>in silico</jats:italic> substitution studies enable us to establish the prospects of some Cp<jats:sup>−</jats:sup> anion derivatives to further improve the oxidative stability, but still the Mg<jats:sup>2+</jats:sup> solvation must be monitored for ease of reduction and Mg plating.</jats:p>