Core-Shell Structure and Interaction Mechanism of γ-MnO₂ Coated Sulfur for Improved Lithium-Sulfur Batteries

Lithium-sulfur batteries have attracted worldwide interest due to their high theoretical capacity of 1672 mAh g^-1 and low cost. However, the practical applications are hampered by capacity decay, mainly attributed to the polysulfide shuttle. Here, the authors have fabricated a solid core-shell γ-MnO₂ -coated sulfur nanocomposite through the redox reaction between KMnO₄ and MnSO₄ . The multifunctional MnO₂ shell facilitates electron and Li⁺ transport as well as efficiently prevents polysulfide dissolution via physical confinement and chemical interaction. Moreover, the γ-MnO₂ crystallographic form also provides one-dimensional (1D) tunnels for the Li⁺ incorporation to alleviate insoluble Li₂ S₂ /Li₂ S deposition at high discharge rate. More importantly, the MnO₂ phase transformation to Mn₃ O₄ occurs during the redox reaction between polysulfides and γ-MnO₂ is first thoroughly investigated. The S@γ-MnO₂ composite exhibits a good capacity retention of 82% after 300 cycles (0.5 C) and a fade rate of 0.07% per cycle over 600 cycles (1 C). The degradation mechanism can probably be elucidated that the decomposition of the surface Mn₃ O₄ phase is the cause of polysulfide dissolution. The recent work thus sheds new light on the hitherto unknown surface interaction mechanism and the degradation mechanism of Li-S cells.