Closed‐Pore Engineering Based on Spatiotemporally Partitioned Radical Editing for High‐Performance Hard Carbon Anodes in Sodium‐Ion Batteries

Abstract Hard carbon (HC) is recognized as a superior anode material for sodium‐ion batteries (SIBs), yet the cost‐effective precise regulation of its microstructure continues to present substantial challenges. Herein, a spatiotemporally partitioned radical modulation strategy is proposed, which enables atomic‐level architectural design in asphalt‐derived HC through spatially precise modulation at the molecular scale of radical reactions. Combined molecular dynamics (MD) simulations and experimental analyses reveal that sulfur modification induces molecular slippage effects through edge‐selective hydrogen abstraction, establishing 3D disordered cross‐linked networks. Concurrently, oxygen treatment is shown to generate covalently bonded frameworks through aromatic ring cleavage. The sequential sulfur‐oxygen synergistic strategy enables precise control over graphitic domain evolution trajectories and closed‐pore self‐organization mechanisms, ultimately producing HC materials characterized by abundant closed‐pore architectures, enhanced structural disorder, and minimized specific surface area. The optimized HC exhibits a reversible capacity of 316.67 mAh g −1 with 86.39% initial coulombic efficiency (ICE) in ester‐based electrolytes, complemented by exceptional cycling stability (no capacity degradation over 1500 cycles at 300 mA g −1 ). This study not only elucidates fundamental mechanisms governing asphalt‐based HC precursor modification but also establishes a robust theoretical framework for developing low‐cost, high‐performance SIB energy storage systems.