Engineering a Dual‐Functional Polyarylether Nitrile Nanofibrous Framework for Stable Lithium Metal Anodes in Low N/P Lithium Metal Anodes

While lithium metal holds potential as the anode for advanced lithium sulfur batteries, its practical application is hampered by various challenges such as uncontrolled dendrite growth, significant volume changes and interfacial instability. In this study, a polyarylether nitrile‐based 3D nanofibrous (NF) framework engineered with lithophilic nitrile (─CN) and sulfonic acid (─SO3⁻) moieties is developed. This dual‐functional design enhances lithium ion (Li+) coordination and electrostatic enrichment, homogenizing Li+ flux while stabilizing the electric field at the interface. The electrospinning NF scaffold conformally coats current collectors, serving as a structural buffer to spatially confine lithium plating and reinforce the solid electrolyte interphase. Symmetric cells with NF‐modified anodes achieve stable cycling over 2500 h at 8 mA cm⁻2. In Li–S full cells (N/P ≈ 3), capacity retention reaches 92.9% after 550 cycles at 0.5C, while a pouch cell with 135 mg sulfur loading maintains 814.3 mAh g⁻1 after 60 cycles at 1C. The framework's universal efficacy is further validated in lithium metal batteries with LiFePO4 and LiNi0.8Co0.1Mn0.1O2 cathodes. By synergizing molecular lithiophilicity with 3D architectural control, this work provides a scalable strategy to stabilize lithium anodes under constrained inventories, advancing practical high‐energy‐density batteries.