The polysulfide (PS) dissolution and low conductivity of lithium sulfides (Li2 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 Li2 S, lithium disulfide (Li2 S2 ) evolutions are always overlooked. Herein, Li2 S2 evolutions are monitored from the operando measurements on the pouch cell level. Results indicate that Li2 S2 undergoes slow electrochemical reduction and chemical disproportionation simultaneously during the discharging process, leading to further PS dissolution and Li2 S generation without capacity contribution. Compared with the fully oxidized Li2 S, Li2 S2 still residues at the end of the charging state. Therefore, instead of the considered Li2 S and PSs, slow electrochemical conversions and side chemical reactions of Li2 S2 are the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li-S batteries.
Keywords: Chemical Reactions; Conductive Interlayer; Lithium Disulfides; Lithium Sulfur Battery; Operando Measurement.
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