Compositionally Sequenced Interfacial Layers for High‐Energy Li‐Metal Batteries

Abstract Electrolyte additives with multiple functions enable the interfacial engineering of Li‐metal batteries (LMBs). Owing to their unique reduction behavior, additives exhibit a high potential for electrode surface modification that increases the reversibility of Li‐metal anodes by enabling the development of a hierarchical solid electrolyte interphase (SEI). This study confirms that an adequately designed SEI facilitates the homogeneous supply of Li+, nonlocalized Li deposition, and low electrolyte degradation in LMBs while enduring the volume fluctuation of Li‐metal anodes on cycling. An in‐depth analysis of interfacial engineering mechanisms reveals that multilayered SEI structures comprising mechanically robust LiF‐rich species, electron‐rich P–O species, and elastic polymeric species enabled the stable charge and discharge of LMBs. The polymeric outer SEI layer in the as‐fabricated multilayered SEI could accommodate the volume fluctuation of Li‐metal anodes, significantly enhancing the cycling stability Li||LiNi0.8Co0.1Mn0.1O2 full cells with an electrolyte amount of 3.6 g Ah−1 and an areal capacity of 3.2 mAh cm−2. Therefore, this study confirms the ability of interfacial layers formed by electrolyte additives and fluorinated solvents to advance the performance of LMBs and can open new frontiers in the fabrication of high‐performance LMBs through electrolyte‐formulation engineering.