Bi Nanospheres Embedded in N‐Doped Carbon Nanowires Facilitate Ultrafast and Ultrastable Sodium Storage

Abstract Sodium ion batteries (SIBs) are considered as the ideal candidates for the next generation of electrochemical energy storage devices. The major challenges of anode lie in poor cycling stability and the sluggish kinetics attributed to the inherent large Na + size. In this work, Bi nanosphere encapsulated in N‐doped carbon nanowires (Bi@N‐C) is assembled by facile electrospinning and carbonization. N‐doped carbon mitigates the structure stress/strain during alloying/dealloying, optimizes the ionic/electronic diffusion, and provides fast electron transfer and structural stability. Due to the excellent structure, Bi@N‐C shows excellent Na storage performance in SIBs in terms of good cycling stability and rate capacity in half cells and full cells. The fundamental mechanism of the outstanding electrochemical performance of Bi@N‐C has been demonstrated through synchrotron in‐situ XRD, atomic force microscopy, ex‐situ scanning electron microscopy (SEM) and density functional theory (DFT) calculation. Importantly, a deeper understanding of the underlying reasons of the performance improvement is elucidated, which is vital for providing the theoretical basis for application of SIBs.