Development of a Mg/O ReaxFF Potential to describe the Passivation Processes in Magnesium‐Ion Batteries

One of the key challenges preventing the breakthrough of magnesium‐ion batteries (MIB) is the formation of a passivating boundary layer at the Mg anode. To describe the initial steps of Mg anode degradation by O(2) impurities, a Mg/O ReaxFF (force field for reactive systems) parameter set was developed capable of accurately modeling the bulk, surface, adsorption, and diffusion properties of metallic Mg and the salt MgO. It is shown that O(2) immediately dissociates upon first contact with the Mg anode (modeled as Mg(0001), Mg(10 [Formula: see text] 0)A, and Mg(10 [Formula: see text] 1)), heating the surface to several 1000 K. The high temperature assists the further oxidation and forms a rock salt interphase intersected by several grain boundaries. Among the Mg surface terminations, Mg(10 [Formula: see text] 0)A is the most reactive, forming an MgO layer with a thickness of up to 25 Å. The trained force field can be used to model the ongoing reactions in Mg–air batteries but also to study the oxidation of magnesium metal in general.