Mesoscale Elucidation of Surface Passivation in the Li-Sulfur Battery Cathode.

The cathode surface passivation caused by Li2S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li2S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li2S film on carbon cathode surface. Li2S film growth experiences nucleation, isolated Li2S island growth and island coalescence. The slow adsorption rate at small S2- concentration inhibits the formation of nucleation seeds and the lateral growth of Li2S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li2S nucleation seeds form in such an operating temperature range, thereby facilitating heterogeneous growth and potentially inhibiting the lateral growth of the Li2S film, which may ultimately result in reduced surface passivation. The high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.