The Non-SEI Nature of the Magnesium Metal Anode Interphase in Chloride-based Glyme Electrolytes

Abstract

Magnesium metal anodes offer a promising pathway for high-energy-density post-lithium batteries, but their practical application is hindered by a poorly understood electrode-electrolyte interphase. While lithium metal anodes operate via an ionically conductive and electronically resistive SEI, it remains unclear if magnesium operates under similar principles. We demonstrate that the surface film formed on magnesium in chloride-based glyme electrolytes is fundamentally distinct from a traditional SEI. By combining electrochemical impedance spectroscopy with focused ion beam scanning electron microscopy (FIB-SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), we identify a dual-layer interphase consisting of a thick, porous outer layer and a thin (~10 nm), compact inner layer. Crucially, we present electrochemical and morphological evidence—including identical-location microscopy of deposits and polysulfide probe measurements—proving that this compact layer is ionically insulating but electronically conductive. Consequently, magnesium plating occurs on top of the passivation layer via electron tunneling, whereas stripping requires the mechanical rupture of the film. This inherent asymmetry and the "anti-SEI" nature of the magnesium interphase challenge current interface engineering strategies and suggest that future improvements must address the electronic leakage and mechanical instability of the surface film.