This study investigates the role of microporous carbons and carbonate-based electrolytes in addressing challenges related to polysulfides dissolution and electrolyte compatibility in lithium–sulfur (Li–S) batteries. By employing microporous carbons and varying the sulfur content, we investigate the formation of the cathode-electrolyte interphase (CEI) during the first discharge process. We propose an electrochemical nucleophilic mechanism for the formation of the CEI involving polysulfides and solvent molecules in the confined small pores of the cathode. This interphase, primarily composed of LiF, effectively seals the carbon pores, preventing further solvent intrusion and stabilizing the system. Furthermore, it allows the use of wider pores without compromising the system. Our findings reveal that an increased sulfur content within the micropores enhances cycling stability, contradicting trends observed in ether-based systems. These insights highlight the potential of designing Li–S systems with optimized pore structures and electrolyte compositions to achieve greater stability and capacity retention, marking a significant step forward in the development of practical Li–S batteries.
ACS Applied Energy Materials , 2026, 9 211-221.