Direct Visualization of Lithium Polysulfides and Their Suppression in Liquid Electrolyte.

Understanding of lithium polysulfide (Li-PS) formation and the shuttle phenomenon is essential for practical application of the lithium/sulfur (Li/S) cell, which has superior theoretical specific energy (2600 Wh/kg). However, it suffers from the lack of direct observation on behaviors of soluble Li-PS in liquid electrolytes. Using in situ graphene liquid cell electron microscopy, we have visualized formation and diffusion of Li-PS simultaneous with morphological and phase evolutions of sulfur nanoparticles during lithiation. We found that the morphological changes and Li-PS diffusion are retarded by ionic liquid (IL) addition into electrolyte. Chronoamperometric shuttle current measurement confirms that IL addition lowers the experimental diffusion coefficient of Li-PS by 2 orders of magnitude relative to that in IL-free electrolyte and thus suppresses the Li-PS shuttle current, which accounts for better cyclability and Coulombic efficiency of the Li/S cell. This study provides significant insights into electrolyte design to inhibit the polysulfide shuttle phenomenon.