Directing (110) Oriented Lithium Deposition through High‐flux Solid Electrolyte Interphase for Dendrite‐free Lithium Metal Batteries

Abstract Controlling lithium (Li) electrocrystallization with preferred orientation is a promising strategy to realize highly reversible Li metal batteries (LMBs) but lack of facile regulation methods. Herein, we report a high‐flux solid electrolyte interphase (SEI) strategy to direct (110) preferred Li deposition even on (200)‐orientated Li substrate. Bravais rule and Curie‐Wulff principle are expanded in Li electrocrystallization process to decouple the relationship between SEI engineering and preferred crystal orientation. Multi‐spectroscopic techniques combined with dynamics analysis reveal that the high‐flux CF 3 Si(CH 3 ) 3 (F 3 ) induced SEI (F 3 ‐SEI) with high LiF and −Si(CH 3 ) 3 contents can ingeniously accelerate Li + transport dynamics and ensure the sufficient Li + concentration below SEI to direct Li (110) orientation. The induced Li (110) can in turn further promote the surface migration of Li atoms to avoid tip aggregation, resulting in a planar, dendrite‐free morphology of Li. As a result, our F 3 ‐SEI enables ultra‐long stability of Li||Li symmetrical cells for more than 336 days. Furthermore, F 3 ‐SEI modified Li can significantly enhance the cycle life of Li||LiFePO 4 and Li||NCM811 coin and pouch full cells in practical conditions. Our crystallographic strategy for Li dendrite suppression paves a path to achieve reliable LMBs and may provide guidance for the preferred orientation of other metal crystals.