High Proportion of Active Nitrogen-Doped Hard Carbon Based on Mannich Reaction as Anode Material for High-Performance...

The potential for energy storage in carbonaceous materials is well known. Heteroatom doping - particularly nitrogen doping - can further enhance their electrochemical performance. The type of N configuration determines the reactivity of doped carbon. It remains a challenge, however, to achieve a high ratio of active N (N-5) in N-doped carbon. In this study, a high proportion of active nitrogen-doped hard carbon (PTA-Lys-800) is synthesized by the classical Mannich reaction, using tannic acid (TA) and amino acid as precursors. For sodium-ion batteries (SIBs), PTA-Lys-800 provides outstanding cycling stability and rate performance (338.8 mAh g^-1 at 100 mA g^-1 for 100 cycles, a capacity retention of 86 %; 131.1 mAh g^-1 at 4 A g^-1 after 5000 cycles). The excellent performance of PTA-Lys-800 is attributed to stable hierarchical pore structure, abundant defects, and a high proportion of N-5 formed during the carbonization process. Based on a detailed fundamental analysis, the pseudocapacitance mechanism is found to contribute to the higher sodium storage process in PTA-Lys-800. The Na-adsorption mechanism is further explored through ex situ Raman spectroscopy. A new method is presented for designing carbonaceous anode materials with high capacity and long cycle life.