Li-Se battery is a promising energy storage candidate owing to its high theoretical volumetric capacity and safe operating condition. In this work, for the first time, we report using the whole organic Melamine-based porous polymer networks (MPNs) as a precursor to synthesize a N, O, S co-doped hierarchically porous carbon nanobelts (HPCNBs) for both Li-ion and Li-Se battery. The N, O, S co-doping resulting in the defect-rich HPCNBs provides fast transport channels for electrolyte, electrons and ions, but also effectively relieve volume change. When used for Li-ion battery, it exhibits an advanced lithium storage performance with a capacity of 345 mAh g−1 at 500 mA g−1 after 150 cycles and a superior rate capacity of 281 mAh g−1 even at 2000 mA g−1. Further density function theory calculations reveal that the carbon atoms adjacent to the doping sites are electron-rich and more effective to anchor active species in Li-Se battery. With the hierarchically porous channels and the strong dual physical–chemical confinement for Li2Se, the Se@ HPCNBs composite delivers an ultra-stable cycle performance even at 2 C after 1000 cycles. Our work here suggests that introduce of heteroatoms and defects in graphite-like anodes is an effective way to improve the electrochemical performance.
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