Understanding the Sodium Storage Behavior of Closed Pores/Carbonyl Groups in Hard Carbon

Hard carbon (HC) is a promising anode material for sodium-ion batteries. However, the intrinsic relationship between the closed pores/surface groups and sodium storage performance has been unclear, leading to difficulties in targeted regulation. In this study, renewable tannin extracts were used as raw materials to prepare HC anodes with abundant tunable closed pores and carbonyl groups through a pyrolytic modulation strategy. Combining ex situ characterizations reveals that closed pores and carbonyl groups are regulated by the pyrolytic process. Further, it is demonstrated that the plateau region is mainly contributed by the closed pores; highly stable fluorine-rich solid electrolyte interphase compositions are produced through carbonyl-induced interfacial catalysis. The optimized HC anode displays good cycling stability, exhibiting a high reversible capacity (360.96 mAh g^-1) at 30 mA g^-1 and capacity retention of up to 94% after 500 cycles at 1 A g^-1. Moreover, the full battery assembled with Na₃V₂(PO₄)₃/C demonstrates a stable cycling performance. These findings provide a fresh knowledge of the structural design of high-performance HC anode materials and the mechanism of sodium storage in HC.