Designing a Safe Electrolyte Enabling Long‐Life Li/S Batteries

Lithium–sulfur (Li/S) batteries suffer from “shuttle” reactions in which soluble polysulfide species continuously migrate to and from the Li metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit the practical applications of Li/S batteries. LiNO 3 has been proposed as an electrolyte additive to reduce the shuttle reactions by aiding the formation of a stable solid electrolyte interphase (SEI) at the Li metal, limiting polysulfide shuttling. However, LiNO 3 is continuously consumed during cycling, especially at low current rates. Therefore, the Li/S battery cycle life is limited by the LiNO 3 concentration in the electrolyte. In this work, an ionic liquid (IL) [ N ‐methyl‐( n ‐butyl)pyrrolidinium bis(trifluoromethylsulfonyl)imide] was used as an additive to enable longer cycle life of Li/S batteries. By tuning the IL concentration, an enhanced stability of the SEI and lower flammability of the solutions were demonstrated, that is, higher safety of the battery. The Li/S cell built with a high sulfur mass loading (4 mg cm −2 ) and containing the IL‐based electrolyte demonstrated a stable capacity of 600 mAh g −1 for more than double the number of cycles of a cell containing LiNO 3 additive.