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.