A Dealloying Synthetic Strategy for Nanoporous Bismuth-Antimony Anodes for Sodium Ion Batteries

Metal-based anodes have recently aroused much attention in sodium ion batteries (SIBs) owing to their high theoretical capacities and low sodiation potentials. However, their progresses are prevented by the inferior cycling performance caused by severe volumetric change and pulverization during the (de)sodiation process. To address this issue, herein an alloying strategy was proposed and nanoporous bismuth (Bi)-antimony (Sb) alloys were fabricated by dealloying of ternary Mg-based precursors. As an anode for SIBs, the nanoporous Bi₂Sb₆ alloy exhibits an ultralong cycling performance (10 000 cycles) at 1 A/g corresponding to a capacity decay of merely 0.0072% per cycle, due to the porous structure, alloying effect and proper Bi/Sb atomic ratio. More importantly, a (de)sodiation mechanism ((Bi,Sb) ↔ Na(Bi,Sb) ↔ Na₃(Bi,Sb)) is identified for the discharge/charge processes of Bi-Sb alloys by using operando X-ray diffraction and density functional theory calculations.