Summary
Bismuth has garnered attention as a promising anode material for Na‐ion batteries (NIBs) because of its high volumetric capacity and appropriate operating potential. However, the large and repeated volume variations of the Bi anode during sodiation/desodiation lead to a poor electrochemical performance; thus, a rational design for Bi‐based materials is essential for their application to NIB anodes. First, the Na reaction pathway of Bi was analyzed using various cutting‐edge ex situ analysis tools. Subsequently, two different types of Bi‐based nanocomposite materials were prepared to enhance the Na storage performance of Bi: one is an amorphous carbon (a‐C)‐modified Bi nanocomposite (Bi@a‐C) fabricated via mechanical treatment and the other is a metal–organic framework (MOF)‐derived polyhedral Bi nanocomposite (p‐Bi@C) fabricated via chemical treatment. The Na storage performance of p‐Bi@C is much higher than that of Bi@a‐C because of the homogeneous anchoring effect of Bi nanocrystals in the MOF‐derived polyhedral C matrices, which have robust and high Na‐ion conduction. The p‐Bi@C delivered a highly reversible capacity (302 mAh g−1 over 100 cycles) and high rate capability (205 mAh g−1 at 2C). Therefore, this study provides a rational design of Bi‐based nanocomposite materials for application to high‐performance NIB anodes.
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