Sea urchin-like hierarchical structured Ag-doped MnO2 cathode material for stable aqueous zinc-ion batteries
摘要
Rechargeable aqueous zinc-ion batteries (RAZIBs) have emerged as promising candidates for large-scale energy storage systems, owing to their low cost, high safety, and environmental benignity. However, their practical application is hindered by intrinsic limitations of cathode materials, including sluggish Zn2+ diffusion kinetics, poor electrical conductivity, and structural degradation during cycling. Herein, we report a facile hydrothermal strategy to synthesize Ag-doped MnO2 cathode with uniform urchin-like nanostructures surrounded by nanowires as high-performance cathodes for RAZIBs. The optimal 5 wt% Ag doping yields denser nanowire arrays, namely 5Ag/MnO2, increases accessible active sites, and introduces lattice defects while preserving the tetragonal MnO2 crystal structure (I4/m). The electrochemical characterization demonstrated that 5Ag/MnO2 exhibited significantly enhanced kinetics, including lower charge-transfer resistance, reduced polarization, and higher Zn2+ diffusion coefficient. Consequently, the 5Ag/MnO2 cathode delivered a high initial discharge capacity of 153.4 mAh g−1 at 1 A g−1 and superior long-term cycling stability (the discharge specific capacity remained at 135.5 mAh g−1 and 88.3% capacity retention after 500 cycles). Mechanism studies via ex situ XRD, XPS, and CV reveal a reversible Zn2+/H+ storage mechanism involving phase transformation between MnO2 and ZnMn2O4, with mixed capacitive and intercalation behavior. The enhanced performance is attributed to Ag doping facilitating rapid ion diffusion, improving electronic conductivity, and stabilizing the hierarchical structure. This work provides a viable strategy for designing high-performance MnO2-based cathodes for advanced zinc-ion batteries, advancing the practical application of RAZIBs.