Stable Liquid-Sulfur Generation on Transition-Metal Dichalcogenides toward Low-Temperature Lithium-Sulfur Batteries

The electrochemical formation of liquid sulfur at room temperature on the basal plane of MoS₂ has attracted much attention due to the high areal capacity and rapid kinetics of lithium-liquid sulfur chemistry. However, the liquid sulfur is converted to the solid phase once it contacts the solid sulfur crystals generated from the edge of MoS₂. Thus, stable liquid sulfur cannot be formed on the entire MoS₂ surface. Herein, we report entire liquid sulfur generation on hydrogen-annealed MoS₂ (H₂-MoS₂), even under harsh conditions of large overpotentials and low working temperatures. The origins of the solely liquid sulfur formation are revealed to be the weakened interactions between H₂-MoS₂ and sulfur molecules and the decreased electrical polarization on the edges of the H₂-MoS₂. Progressive nucleation and droplet-merging growth behaviors are observed during the sulfur formation on H₂-MoS₂, signifying high areal capacities by releasing active H₂-MoS₂ surfaces. To demonstrate the universality of this strategy, other transition-metal dichalcogenides (TMDs) annealed in hydrogen also exhibit similar sulfur growth behaviors. Furthermore, the H₂ annealing treatment can induce sulfur vacancies on the basal plane and partial oxidation on the edge of TMDs, which facilitates liquid sulfur formation. Finally, liquid sulfur can be generated on H₂-MoS₂ flakes at an ultralow temperature of -50 °C, which provides a possible development of low-temperature lithium-sulfur batteries. This work demonstrates the potential of a pure liquid sulfur-lithium electrochemical system using functionalized two-dimensional materials.