Direct Monitoring of Li2S2 Evolution and Its Influence on the Reversible Capacities of Lithium‐Sulfur Batteries

Abstract The polysulfide (PS) dissolution and low conductivity of lithium sulfides (Li 2 S) are generally considered the main reasons for limiting the reversible capacity of the lithium‐sulfur (Li‐S) system. However, as the inevitable intermediate between PSs and Li 2 S, lithium disulfide (Li 2 S 2 ) evolutions are always overlooked. Herein, Li 2 S 2 evolutions are monitored from the operando measurements on the pouch cell level. Results indicate that Li 2 S 2 undergoes slow electrochemical reduction and chemical disproportionation simultaneously during the discharging process, leading to further PS dissolution and Li 2 S generation without capacity contribution. Compared with the fully oxidized Li 2 S, Li 2 S 2 still residues at the end of the charging state. Therefore, instead of the considered Li 2 S and PSs, slow electrochemical conversions and side chemical reactions of Li 2 S 2 are the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li‐S batteries.