Correlations between Precipitation Reactions and Electrochemical Performance of Lithium–Sulfur Batteries

A comprehensive description of the electrochemical processes in the positive electrode of lithium–sulfur batteries is crucial for the enhancement of sulfur utilization. However, the discharge mechanisms are complicated due to the various reactions in multiple phases and the tortuosity of the highly porous carbon matrix. While previous studies have focused on the precipitation of lithium sulfide, the effect of the limited mass transport inside the micropores and mesopores of an electrode with optimized surface area have largely been neglected. In this work, in-operando small-angle scattering with three different contrasts, and wide-angle scattering measurements are made while the internal and diffusion resistances are measured simultaneously. The results indicate that the precipitates grow mostly in number, not in size, and that the structure of the carbon matrix is not affected. The comparison of the small-angle and wide-angle scattering reveals the amorphous discharge products found at a low discharge rate. Further analyses demonstrate the correlation between the diffusion resistance and the composition of material in the mesopores at the end of discharge, which suggests that Li-ion deficiency is the limiting factor of sulfur utilization at a medium discharge rate.