Abstract

AbstractMicro‐sized bismuth (Bi) is recognized for its high volumetric capacity and suitable working potential, making it a promising anode candidate for sodium‐ion batteries (SIBs). However, its substantial volume changes and slow reaction kinetics during cycling detrimentally affects the SIB performance. Theoretical prediction uncovers a previously unexplored favorable attribute that bonding between nitrogen within a carbon coating and Bi atoms facilitates Na+ ingress into the Bi bulk, significantly enhancing Bi‐Na alloying reactions, mitigating volume expansion, and preventing Na‐dendrite formation. Experimentally, the study innovatively engineers a flower‐like micro‐sized Bi encapsulated within an elastic, nitrogen‐doped carbon framework (FBi@NC) working as an efficient anode for SIBs. This design enables FBi@NC anode achieving a high tap density of 2.86 g cm−3 and delivering a remarkable volumetric capacity of 1100 mAh cm−3 at 1 mA cm−2. It also exhibits exceptional rate capability (368.2 mA h g−1 at 30 A g−1) and super durable cyclability (10 000 cycles with 318.8 mA h g−1 at 5 A g−1, retaining 82% capacity). Full cells with Na3V2(PO4)3 cathodes demonstrate superior rate and cycling performances. Crucially, this study elucidates the underlying Na+‐storage mechanisms and the contributory factors to performance enhancement, providing vital insights for the development of high‐energy and stable SIBs.

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