eloped which has achieved high reversible capacity and Coulombic efficiency to fulfill practical application.20:T413,A porous hard carbon material was synthesized by the simple pyrolysis of H3PO4-treated biomass, i.e., pomelo peels, at 700 °C in N2. The as-obtained hard carbon had a 3D connected porous structure and a large specific surface area of 1272 m2 g−1. XPS analysis showed that the carbon material was functionalized by O-containing and P-containing groups. The porous hard carbon was used as an anode for sodium ion batteries and exhibited good cycling stability and rate capability, delivering a capacity of 181 mA h g−1 at 200 mA g−1 after 220 cycles and retaining a capacity of 71 mA h g−1 at 5 A g−1. The sodium storage mechanisms of the porous hard carbon can be explained by Na+ intercalation into the disordered graphene layers, redox reaction of the surface O-containing functional groups and Na+ storage in the nanoscale pores. However, the porous hard carbon demonstrated a low coulombic efficiency of 27%, resulting from the formation of a solid electrolyte interphase film and the side reactions of surface phosphorus groups.21:T4bb,Phosphorus-doped hard carbon nanofibers with macroporous structure were successfully synthesized by electrospinning followed by a thermal treatment process using polyacrylonitrile and H₃PO₄ as carbon and phosphorus precursors, respectively. X-ray photoelectron spectroscopy analysis reveals that the doped phosphorus atoms can incorporate into the carbon framework and most of them are connecting with carbon atoms to form P-C bond. The (002) plane interlayer spacing was taken from the X-ray diffraction pattern, which shows a large spacing of 3.83 Å for the obtained P-doped hard carbon nanofibers. When used as an anode in sodium-ion batteries, the as-prepared P-doped hard carbon nanofibers can deliver a reversible capacity of 288 and 103 mAh g^-1 at a current density of 50 mA g^-1 and 2 A g^-1, respectively. After 200 cycles at 50 mA g^-1, the capacity retention of P-doped hard carbon nanofibers still reaches 87.8%, demonstrating good cycling durability. These excellent electrochemical performances of P-doped hard carbon nanofibers can be attributed to the macroporous structure, large interlayer spacing, and the formation of P-C bond.

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