Tailored Regulation of Graphite Microcrystals via Tandem Catalytic Carbonization for Enhanced Electrochemical Performance of Hard Carbon in the Low‐Voltage Plateau

Abstract The sodium storage behavior in the plateau region is crucial for determining the capacity and rate capability of hard carbon (HC) anodes in sodium‐ion batteries (SIBs). Key structural features for achieving excellent plateau performance include extended graphite domains and increased interlayer spacing. However, synchronously optimizing these two structures is challenging due to their inherent trade‐off. Herein, a tandem catalytic carbonization strategy is developed to construct HC with long graphite domains (L a = 5.31 nm) and large interlayer spacing (d 002 = 0.389 nm) simultaneously. Comprehensive in situ and ex situ tests unravel the catalytic selective bond breaking and aromatization effects of ZnCl 2 , the catalytic graphitic layers enlargement and occupied effects of formed ZnO and Zn in different temperature stages, leading to the formation of the unique structure. The optimal HCZ‐0.1 exhibits a high reversible capacity of 346.9 mAh g −1 with a plateau capacity of 249.4 mAh g −1 , and high‐rate performance (114.0 mAh g −1 at 5 A g −1 ). In addition, the sodium storage mechanism and origin of enhanced Na + kinetics of HCZ‐0.1 are also revealed. This work offers a precise method to engineer the graphite microcrystal structure in HC for superior sodium storage in the plateau region.