AbstractThe reaction between polysulfides and a lithium anode in a Li–S battery was examined using HPLC. The results demonstrated that the polysulfide species with six sulfur atoms or more were reactive with regard to lithium metal. Although the reaction can be greatly inhibited by the addition of LiNO3 in the electrolyte, LiNO3 cannot form a stable protection layer on the Li anode to prevent the reaction during storage.