Unveiling Intrinsic Potassium Storage Behaviors of Hierarchical Nano Bi@N‐Doped Carbon Nanocages Framework via In Situ Characterizations

Metallic bismuth has drawn attention as a promising alloying anode for advanced potassium ion batteries (PIBs). However, serious volume expansion/electrode pulverization and sluggish kinetics always lead to its inferior cycling and rate properties for practical applications. Therefore, advanced Bi‐based anodes via structural/compositional optimization and sur‐/interface design are needed. Herein, we develop a bottom‐up avenue to fabricate nanoscale Bi encapsulated in a 3D N‐doped carbon nanocages (Bi@N‐CNCs) framework with a void space by using a novel Bi‐based metal‐organic framework as the precursor. With elaborate regulation in annealing temperatures, the optimized Bi@N‐CNCs electrode exhibits large reversible capacities and long‐duration cyclic stability at high rates when evaluated as competitive anodes for PIBs. Insights into the intrinsic K+‐storage processes of the Bi@N‐CNCs anode are put forward from comprehensive in situ characterizations. A hierarchical nano Bi@N‐doped carbon nanocage framework with an interior void space was smartly fabricated as competitive anode for K‐ion batteries. Its intrinsic potassium storage behaviors are unveiled via comprehensive in situ characterizations.