Effect of the Electrolyte Solvent on Redox Processes in Mg-S Batteries

Mg-S batteries are attractive for next-generation energy storage because of their high theoretical capacity and low cost. The foremost challenge in Mg-S batteries is designing electrolytes that support reversible electrochemistry at both electrodes. Here, we target a solution-mediated reduction pathway for the S₈ cathode by tailoring the electrolyte solvent. Varying the solvent in Mg-based systems is complicated because of the active nature of the solvent in solvating Mg²⁺ and the complex dynamics of electrolyte-Mg interfaces. To understand the effect of the solvent on the S₈ reduction processes in the Mg-S cell, the magnesium-aluminum chloride complex (MACC) electrolyte was prepared in different ethereal solvents. Reversible Mg electrodeposition is demonstrated in the MACC electrolyte in several solvent systems. The electrodeposition overpotentials and current densities are found to vary with the solvent, suggesting that the solvent plays a noninnocent role in the electrochemical processes at the Mg interface. Mg-S cells are prepared with the electrolytes to understand how the solvent affects the reduction of S₈. A reductive wave is present in all linear-sweep voltammograms, and the peak potential varies with the solvent. The peak potential is approximately 0.8 V versus Mg/Mg²⁺, lower than the expected reduction potential of 1.7 V. We rule out passivation of the Mg anode as the cause for the low voltage peak potential, making processes at the S₈ cathode the likely culprit. The ability to oxidize MgS with the MACC electrolyte is also examined, and we find that  the oxidation current can be attributed to side reactions at the C-electrolyte interface.