3D Nanotubular Nanoporous N-Doped Graphene with Curvature-Induced Zincophilicity for Ultrafast and Dendrite-Free Zn Deposition

Dendrite-free Zn anodes enabling stable cycling at high current densities and capacities remain a critical challenge for zinc-based energy storage. Here, we report a 3D free-standing nanotubular nanoporous N-doped graphene (np-NG) network doped with ultrathin Bi₂O₃ sheets (np-NG/Bi) as ultrahigh-capacity anode host. The lightweight, binder- and current-collector-free host enables uniform, rapid Zn deposition with near-complete volume utilization. Owing to its mechanical robustness, high conductivity, and large surface area, free-standing np-NG/Bi sustains stable cycling for 4000 h at 5 mA cm^–2 (5 mAh cm^–2) and over 600 h at 50 mA cm^–2 (10 mAh cm^–2). The high rate performance is attributed to the highly curved graphene nanotubular architecture and curvature-induced zincophilicity surfaces, which enable a rapid, tube interior-first, and dendrite-free Zn²⁺ deposition. The superior performance of np-NG/Bi is further demonstrated in Zn-ion and Zn–air batteries, highlighting a 3D graphene design strategy for high-performance Zn metal anodes in next-generation energy systems.