Regulating Li Plating/Stripping by Synergistic Dual‐Alloy Modification and Robust LiF‐Rich Interface for High‐Performance Li Metal Batteries

ABSTRACT Practical application of Li metal anodes (LMAs) is primarily impeded by Li dendrite growth and interface instability. Securing reversible Li plating/stripping and constructing robust solid electrolyte interphase (SEI) are critical to guarantee the cycling stability of LMAs. Herein, an ultra‐thin LMA with LiF‐rich SEI is designed by integrating LiMg and Li 9 Al 4 alloys into a cellulose‐derived carbon/reduced graphene oxide host (C/rGO/MALi). Density functional theory (DFT) calculations elucidate that the alloys synergistically modulate the surface electronic structure, providing abundant lithiophilic active sites, high Li adsorption energy and low ion diffusion barrier to guide uniform Li deposition. Meanwhile, the in‐situ formed LiF establishes high electron tunneling barrier and low Li + diffusion barrier, ensuring the interfacial stability and fast ion transfer. Consequently, the symmetric cell exhibits an excellent cyclability for over 1200 h with a low overpotential of 23 mV at 2 mA cm −2 . When paired with high‐loading LiFePO 4 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes, the full cells achieve remarkable rate performance and cycling stability in both coin cells (131.5 mAh g −1 after 400 cycles at 1 C) and pouch cells (90.3% capacity retention after 90 cycles). This work highlights the rational regulation of anode structure as a viable strategy toward high‐energy‐density Li metal batteries.