Zhu Yirong, Zhao Rui, Xu Yuting, Chen Wenhao, Hu Zhongliang, Xi Liujiang, Xie Yujia, Hou Hongshuai, Liu Tongchao, Amine Khalil, Ji Xiaobo, Zou Guoqiang
College of Materials and Advanced Manufacturing, Hunan University of Technology, Zhuzhou, 412007, China.
College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China.
Adv Mater. 2025 Apr;37(17):e2419582. doi: 10.1002/adma.202419582. Epub 2025 Mar 17.
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@ZnMnO/MXene, and then undergoes a reversible conversion from MnO@ZnMnO/MXene to MnOOH@ZnMnO/MXene, accompanied by the co-insertion/extraction of H and Zn. 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.
作为一种潜在的阴极材料，锰基硫化物因其在水系锌离子存储方面的诸多优势，近年来受到了越来越多的关注。不幸的是，一些挑战，如缓慢的动力学、不稳定的结构以及储能过程中存在争议的相变机制，阻碍了其实际应用。在此，受密度泛函理论（DFT）计算的启发，设计了一种新型的富含硫空位的三维异质结构MnS/MXene气凝胶，并首次将其用作水系锌离子电池/混合电容器（ZIBs/ZICs）的阴极。得益于硫空位和异质结构的协同改性策略，所构建的MnS/MXene//Zn ZIBs表现出显著增强的电化学性能，尤其是出色的倍率性能和循环稳定性。更令人鼓舞的是，组装的MnS/MXene//多孔碳（PC）ZICs表现出超高的能量密度、高功率密度和出色的循环寿命。最值得注意的是，系统的动力学分析、非原位表征和DFT计算表明，MnS/MXene首先不可逆地转化为MnO@ZnMnO/MXene，然后经历从MnO@ZnMnO/MXene到MnOOH@ZnMnO/MXene的可逆转化，同时伴有H和Zn的共嵌入/脱出。本文提出的硫空位和异质结构的协同改性策略以及深入的机理研究，为设计和开发水系锌基储能器件中的高性能阴极提供了有价值的指导。
