Anion Vacancies Coupling with Heterostructures Enable Advanced Aerogel Cathode for Ultrafast Aqueous Zinc‐Ion Storage

Abstract As a potential cathode material, manganese‐based sulfide has recently attracted increasing interest due to its many advantages in aqueous zinc‐ion storage. Unfortunately, some challenges such as sluggish kinetics, unstable structure, and controversial phase transition mechanism during the energy storage process hinder its practical application. Herein, inspired by density functional theory (DFT) calculations, a novel 3D sulfur vacancy‐rich and heterostructured MnS/MXene aerogel is designed, and used as a cathode for aqueous Zn‐ion batteries/hybrid capacitors (ZIBs/ZICs) for the first time. Thanks to the synergistic modification strategy of sulfur vacancies and heterostructures, the as‐constructed MnS/MXene//Zn ZIBs exhibit significantly enhanced electrochemical properties, especially outstanding rate capability and cyclic stability. More encouragingly, the as‐assembled MnS/MXene//porous carbon (PC) ZICs exhibit an ultrahigh energy density, a high power density, and a splendid cycling lifespan. Most notably, systematic kinetic analyses, ex situ characterizations, and DFT calculations illustrate that MnS/MXene first irreversibly converts into MnO_x@ZnMnO₃/MXene, and then undergoes a reversible conversion from MnO_x@ZnMnO₃/MXene to MnOOH@ZnMn₂O₄/MXene, accompanied by the co‐insertion/extraction of H⁺ and Zn²⁺. The synergistic modification strategy of sulfur vacancies and heterostructures and the thorough mechanistic study proposed in this work offer valuable guidance for designing and exploiting high‐performance cathodes in aqueous zinc‐based energy storage devices.