Heteroatom dopants and structural defects exist concurrently and share analogous effects in modifying the electrochemical storage performance of doped hard carbon materials. However, the underlying interplay among the dopants and defects has long been ignored, which leads to controversial conclusions on the influence of dopants in defect-rich hard carbon matrix. Herein, through combined theoretical calculations and electrochemical measurements, the interplay among N, S dopants and carbon vacancy defects and its effect on hard carbon materials’ electrochemical performance for sodium-ion storage are studied. The dopant-defect interplay is corroborated to play crucial roles on the capacity and rate capability of carbon anodes, and co-doping of N, S species is demonstrated as an efficient method. Steered by the calculations, a universal in-situ texturing method is developed to synthesize the N, S dual-doped porous hard carbons with preferential features for sodium-ion batteries. The optimized hard carbon material afforded a large reversible capacity (430 mAh g^-1 at 0.05 A g^-1), an unprecedented rate performance (up to 277 mAh g^-1 at 5 A g^-1), and excellent cycling stability in sodium-ion batteries. The results in this work will inspire the rational design and fabrication of carbon materials with high capacity and superb rate capability for sodium-ion storage.

杂原子掺杂剂和结构缺陷同时存在，并且在改变掺杂的硬碳材料的电化学存储性能方面具有相似的作用。然而，掺杂剂和缺陷之间潜在的相互作用早已被忽略，这导致在富缺陷的硬碳基质中掺杂剂的影响引起有争议的结论。在本文中，通过理论计算和电化学测量相结合的方法，研究了氮，硫掺杂物与碳空位缺陷之间的相互作用及其对硬碳材料钠离子存储电化学性能的影响。证实了掺杂物-缺陷相互作用对碳阳极的容量和倍率性能起着至关重要的作用，并且证明了N，S物种的共掺杂是一种有效的方法。在计算的指导下，通用开发了原位织构方法以合成具有钠离子电池优先功能的N，S双掺杂多孔硬碳。优化的硬质碳材料，得到大的可逆容量（430毫安克^-1 0.05 A G ^-1），以空前的速度性能（高达277毫安克^-1在5 A G ^-1），并在钠优异的循环稳定性离子电池。这项工作的结果将启发合理设计和制造具有高容量和极高速率能力的碳材料用于钠离子存储。