Identifying the Critical Anion–Cation Coordination to Regulate the Electric Double Layer for an Efficient Lithium‐Metal Anode Interface

Abstract The persistent efforts to reveal the formation and evolution mechanisms of solid electrolyte interphase (SEI) are of fundamental significance for the rational regulation. In this work, through combined theoretical and experimental model investigations, we elucidate that the electric double layer (EDL) chemistry at the electrode/electrolyte interface beyond the thermodynamic stability of electrolyte components predominately controls the competitive reduction reactions during SEI construction on Li metal anode. Specifically, the negatively‐charged surface of Li metal will prompt substantial cation enrichment and anion deficiency within the EDL. Necessarily, only the species participating in the solvation shell of cations could be electrostatically accumulated in proximity of Li metal surface and thereafter be preferentially reduced during sustained dynamic cycling. Incorporating multi‐valent cation additives to more effectively drag the favorable anionic SEI enablers into EDL is validated as a promising strategy to upgrade the Li protection performance. The conclusions drawn herein afford deeper understandings to bridge the EDL principle, cation solvation, and SEI formation, shedding fresh light on the targeted regulation of reactive alkali metal interfaces.