Systematic Modification of MoO₃‐Based Cathode by the Intercalation Engineering for High‐Performance Aqueous Zinc‐Ion Batteries

Abstract Aqueous Zn‐ion batteries are attracting extensive attention, but their large‐scale application is prevented by the poor electrochemical kinetics and terrible lifespan. Herein, a strategy of introducing the conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) into the interlayers of α‐MoO₃ is reported to systematically overcome the above shortcomings. Through data analyses of the cyclic coltammetry, electrochemical impedance spectroscopy, and galvanostatic intermittent titration technique, the electrochemical kinetics of the PEDOT‐intercalated MoO₃ (PEDOT‐MoO₃) is proved to be significantly improved. The first‐principles calculations microscopically disclose that the changed energy band and the lowered binding energy between Zn²⁺ and host O²⁻ boost electrochemical kinetics of PEDOT‐MoO₃. Meanwhile, its decreased hydrophilicity and the suppressed dissolution of molybdenum stabilizes the repeated cycling processes. Interestingly, it is found that excellent electrochemical kinetics of cathode electrode can restrain the growth of zinc dendrite on the Zn anode, prolonging the lifespan of aqueous Zn‐ion batteries. As a result, the PEDOT‐MoO₃ exhibits the enhanced specific capacity (341.5 vs 146.7 mAh g⁻¹ at 0.1 A g⁻¹), high rate capacity (178.2 vs 19.4 mAh g⁻¹ at 30 A g⁻¹) and prolonged cycling stability (77.6% capacity retention over 500 cycles vs 2.3% capacity retention over 100 cycles at 30 A g⁻¹) compared with pristine MoO₃. Moreover, the PEDOT‐MoO₃ as cathode of quasi‐solid‐state ZIBs also delivers an impressive electrochemical performance.