Thermodynamics and Kinetics of Sulfur Cathode during Discharge in MgTFSI₂–DME Electrolyte

Abstract Rechargeable magnesium/sulfur battery is of significant interest because its energy density (1700 Wh kg⁻¹ and 3200 Wh L⁻¹) is among the highest of all battery chemistries (lower than Li/O₂ and Mg/O₂ but comparable to Li/S), and Mg metal allows reversible operation (100% Coulombic efficiency) with no dendrite formation. This great promise is already justified in some early reports. However, lack of mechanistic study of sulfur reaction in the Mg cation environment has severely hindered our understanding and prevents effective measures for performance improvement. In this work, the very first systematic fundamental study on Mg/S system is conducted by combining experimental methods with computational approach. The thermodynamics and reaction pathway of sulfur cathode in MgTFSI₂–DME electrolyte, as well as the associated kinetics are thoroughly investigated. The results here reveal that sulfur undergoes a consecutive staging pathway in which the formation and chain‐shortening of polysulfide occur at early stage accompanied by the dissolution of long‐chain polysulfide, and solid‐state transition from short‐chain polysulfide to magnesium sulfide occurs at late stage. The former process is much faster than the latter due to the synergetic effect of the mediating effect of dissolved polysulfide and the fast diffusion of Mg ion in the amorphous intermediate.