Mott-Schottky MXene@WS₂ Heterostructure: Structural and Thermodynamic Insights and Application in Ultra Stable Lithium-Sulfur Batteries

Due to the "shuttle effect" and low conversion kinetics of polysulfides, the cycle stability of lithium sulfur (Li-S) battery is unsatisfactory, which hinders its practical application. The Mott-Schottky heterostructures for Li-S batteries not only provide more catalytic/adsorption active sites, but also facilitate electrons transport by a built-in electric field, which are both beneficial for polysulfides conversion and long-term cycle stability. Here, MXene@WS₂ heterostructure was constructed by in-situ hydrothermal growth for separator modification. In-depth ultraviolet photoelectron spectroscopy and ultraviolet visible diffuse reflectance spectroscopy analysis reveals that there is an energy band difference between MXene and WS₂ , confirming the heterostructure nature of MXene@WS₂ . DFT calculations indicate that the Mott-Schottky MXene@WS₂ heterostructure can effectively promote electron transfer, improve the multi-step cathodic reaction kinetics, and further enhance polysulfides conversion. The built-in electric field of the heterostructure plays an important role in reducing the energy barrier of polysulfides conversion. Thermodynamic studies reveal the best stability of MXene@WS₂ during polysulfides adsorption. As a result, the Li-S battery with MXene@WS₂ modified separator exhibits high specific capacity (1613.7 mAh g^-1 at 0.1 C) and excellent cycling stability (2000 cycles with 0.0286 % decay per cycle at 2 C). Even at a high sulfur loading of 6.3 mg cm^-2 , the specific capacity could be retained by 60.0 % after 240 cycles at 0.3 C. This work provides deep structural and thermodynamic insights into MXene@WS₂ heterostructure and its promising prospect of application in high performance Li-S batteries.