Bi-Sb alloys are appealing anode materials for potassium ion batteries (PIBs) but challenged by their enormous volumetric variation during operation. Herein, a facile one-step dealloying protocol was devised and utilized to prepare the Bi-Sb alloys that manifest an exotic bicontinuous hierarchical nanoporous (np) microstructure ideal for volume-change mitigation and K + transport percolation. The growth mechanism fostering the peculiar morphology of the np-(Bi,Sb) alloys was investigated and

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... rified via operando X-ray (XRD) and ex-situ scanning electron microscopy (SEM). In particular, the np-Bi6Sb2 electrode, optimized for comprehensive electrochemical performance, achieves decent reversible capacities and a superior lifespan, as benchmarked with the monometallic references and other Bi-Sb alloy electrodes. The (de)potassiation mechanism of the np-(Bi,Sb) alloys was studied by operando XRD and further rationalized by density functional theory (DFT) calculations, whereby a homogeneous (segregation-free) and robust two-step electrochemically-driven phase transformations' catenation of (Bi,Sb) ↔ K(Bi,Sb)2 ↔ K3(Bi,Sb) was reliably established to substantiate the outstanding reversibility of the np-(Bi,Sb) anodes in PIBs.