Direct Monitoring of Li 2 S 2 Evolution and Its Influence on the Reversible Capacities of Lithium-Sulfur Batteries.

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.
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