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

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 CF₃ Si(CH₃ )₃ (F₃ ) induced SEI (F₃ -SEI) with high LiF and -Si(CH₃ )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 F₃ -SEI enables ultra-long stability of Li||Li symmetrical cells for more than 336 days. Furthermore, F₃ -SEI modified Li can significantly enhance the cycle life of Li||LiFePO₄ 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.