Fluorine‐Rich Lewis Acidic MOF as Ion Modulator to Enable Dendrite‐Free Li Plating for Ah‐Level Li‐Metal Batteries

Lithium metal stands as the most promising anode material to drive the development of next‐generation energy storage systems owing to its unparalleled theoretical gravimetric capacity. However, the naturally formed solid electrolyte interphase (SEI) is inadequate to suppress the uncontrolled growth of lithium dendrites, posing the safety concerns for lithium metal batteries (LMBs). Herein, we propose a F‐rich Lewis acid metal‐organic framework (F‐mof) as an anion captor and a cation accelerator to mitigate the concentration polarization and expedite the lithium ion transport at anode‐electrolyte interface. The lithiophilic nature of F‐mof with a 3D open framework facilitates the uniform lithium deposition and mitigates the electrode volume change during extended cycling. This strong Lewis acid‐modified Li anode enables Li||Li symmetric cells to achieve an extended cycle life of 2000 h at a high capacity of 2 mAh cm −2 . The modified LMBs with LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathodes demonstrate the prolonged 700 cycles at 1 C. The NCM811‐pouch cells with a thick cathode (30 mg cm −2 ) achieve a high energy density of 300 Wh kg −1 based on entire pouch weight. Moreover, this work uses a conversion‐type FeF 3 cathode to assemble multilayer pouch cell, achieving a high capacity of 600 mAh for fluoride conversion reaction batteries.