Iodine-Ion-Assisted Galvanic Replacement Synthesis of Bismuth Nanotubes for Ultrafast and Ultrastable Sodium Storage

Bismuth (Bi) has emerged as a promising anode material for fast-charging and long-cycling sodium-ion batteries (SIBs). However, its dramatically volumetric variations during cycling will undesirably cause the pulverization of active materials, severely limiting the electrochemical performance of Bi-based electrodes. Constructing hollow nanostructures is recognized as an effective way to resolve the volume expansion issues of alloy-type anodes but remains a great challenge for metallic bismuth. Here, we report a facile iodine-ion-assisted galvanic replacement approach for the synthesis of Bi nanotubes (NTs) for high-rate, long-term and high-capacity sodium storage. The hollow tubular structure effectively alleviates the structural strain during sodiation/desodiation processes, resulting in excellent structural stability; the thin wall and large surface area enable ultrafast sodium ion transport. Benefiting from the structural merits, the Bi NT electrode exhibits extraordinary rate capability (84% capacity retention at 150 A g–1) and outstanding cycling stability (74% capacity retention for 65,000 cycles at 50 A g–1), which represent the best rate performance and longest cycle life among all reported anodes for SIBs. Moreover, when coupled with the Na3(VOPO4)2F cathode in full cells, this electrode also demonstrates excellent cycling performance, showing the great promise of Bi NTs for practical application. A combination of advanced research techniques reveals that the excellent performance originates from the structural robustness of the Bi NTs and the fast electrochemical kinetics during cycling.