Title: Composite Lithium Metal Anodes with Lithiophilic and Low‐Tortuosity Scaffold Enabling Ultrahigh Currents and Capacities in Carbonate Electrolytes

Abstract: The practical application of lithium metal anode has been hindered by safety and cyclability issues due to the uncontrollable dendrite growth, especially during fast cycling and deep plating/stripping process. Here, a composite Li metal anode supported by periodic, perpendicular, and lithiophilic TiO₂/poly(vinyl pyrrolidone) (PVP) nanofibers via a facial rolling process is reported. TiO₂/PVP nanofibers with good Li affinity provide low‐tortuosity and directly inward Li⁺ transport paths to facilitate Li nucleation and deposition under high areal capacities and current densities. The micrometer‐scale interspaces between TiO₂/PVP walls offer enough space to circumvent the huge volume variation and avoid structure collapsing during the repeated deep Li plating/stripping. The unique structure enables stable cycling under ultrahigh currents (12 mA cm⁻²), and ultra‐deep plating/stripping up to 60 mAh cm⁻² with a long cycle life in commercial carbonate electrolytes. The gassing behavior in operating pouch cells is observed using ultrasonic transmission mapping. When paired with LiFePO₄ (5 mAh cm⁻²), sulfur (3 mAh cm⁻²), and high‐voltage LiNi_0.8Co_0.1Mn_0.1O₂ cathodes, the composite Li anodes deliver remarkably improved rate performance and cycling stability, demonstrating that it could be a promising strategy for balancing high‐energy density and high‐power density in Li metal batteries.