Optimizing the Void Size of Yolk–Shell Bi@Void@C Nanospheres for High-Power-Density Sodium-Ion Batteries

Bismuth (Bi) has been demonstrated as a promising anode for Na-ion batteries (NIBs) because it has high gravimetry (386 mA h g^-1) and volumetric capacity (3800 mA h cm^-3). However, Bi suffers from large volume expansion during sodiation, leading to poor electrochemical performance. The construction of a nanostructure with sufficient void space to accommodate the volume change has been proven effective for achieving prolonged cycling stability. However the excessive void space will definitely decrease the volumetric energy density of the battery. Herein, we design optimized Bi@Void@C nanospheres (Bi@Void@C-2) with yolk-shell structure that exhibit the best cycling performance and enhanced volumetric energy density. The optimized void space not only could buffer the volume change of the Bi nanosphere but also could keep the high volumetric energy density of the battery. The Bi@Void@C-2 shows an excellent rate capacity of 173 mA h g^-1 at ultrahigh current density of 100 A g^-1 and long-cycle life (198 mA h g^-1 at 20 A g^-1 over 10 000 cycles). The origin of the superior performance is achieved through in-depth fundamental studies during battery operation using in situ X-ray diffraction (XRD) and in situ transmission electron microscope (TEM), complemented by theoretical calculations and ex situ TEM observation. Our rational design provides insights for anode materials with large volume variation, especially for conversion type and alloying type mechanism materials for batteries (i.e., Li-ion batteries, Na-ion batteries).