Instability at the Electrode/Electrolyte Interface Induced by Hard Cation Chelation and Nucleophilic Attack

Electrochemistry is necessarily a science of interfacial processes, and understanding electrode/electrolyte interfaces is essential to controlling electrochemical performance and stability. Undesirable interfacial interactions hinder discovery and development of rational materials combinations. By example, we examine an electrolyte, magnesium­(II) bis­(trifluoromethanesulfonyl)­imide (Mg­(TFSI)₂) dissolved in diglyme, next to the Mg metal anode, which is purported to have a wide window of electrochemical stability. However, even in the absence of any bias, using in situ tender X-ray photoelectron spectroscopy, we discovered an intrinsic interfacial chemical instability of both the solvent and salt, further explained using first-principles calculations as driven by Mg²⁺ dication chelation and nucleophilic attack by hydroxide ions. The proposed mechanism appears general to the chemistry near or on metal surfaces in hygroscopic environments with chelation of hard cations and indicates possible synthetic strategies to overcome chemical instability within this class of electrolytes.