Multi‐Bond Coupled Interfacial and Structural Engineering for Highly‐Efficient and Long‐Lasting Potassium Storage

To address the poor cycle stability and limited rate performance of alloy‐type Sb‐based materials during repeated K + alloying/dealloying, a strategy based on synergistic structural and multi‐bond coupling engineering is proposed to construct (MoO 2 /Sb)@NC hollow octahedra through in situ ion exchange and annealing processes. The systematic experimental studies and theoretical calculations reveal that the Mo─O─C and Sb─O─C double bridge bonds formed at the interface can induce a strong electronic coupling effect, promoting the hybridization of Mo 4d/Sb 5p orbitals with C 2p orbitals and increasing the density of electronic states near the Fermi level. Consequently, the electronic and ionic transport capacity of (MoO 2 /Sb)@NC are considerably improved. Meanwhile, the hollow octahedron and N‐doped carbon prevent the aggregation of Sb, mitigate the volume variation, and improve the structural integrity, which can be confirmed by the results of finite element simulations. These merits endow the (MoO 2 /Sb)@NC anode with impressive electrochemical K + ion storage properties, delivering excellent rate capability and high cycling stability of 166.8 mAh g −1 after 3000 cycles at 1.0 A g −1 . Additionally, the assembly of (MoO 2 /Sb)@NC//PTCDA full‐cells confirms the feasibility of practical application. This work provides universal theoretical guidance and a feasible strategy for advanced materials in potassium‐ion batteries.