Confronting Sulfur Electrode Passivation and Li Metal Electrode Degradation in Lithium‐Sulfur Batteries Using Thiocyanate Anion

Abstract Salt anions with a high donor number (DN) enable high sulfur utilization in lithium‐sulfur (Li‐S) batteries by inducing three‐dimensional (3D) Li 2 S growth. However, their insufficient compatibility with Li metal electrodes limits their cycling stability. Herein, a new class of salt anion, thiocyanate (SCN − ), is presented, which features a Janus character of electron donor and acceptor. Due to a strong Li + coordination by SCN − and the direct interaction of SCN − with polysulfide anions, the LiSCN electrolyte has a remarkably high lithium polysulfide solubility. This electrolyte induces 3D Li 2 S formation and ameliorates cathode passivation, even more than Br − , a typical high DN anion. Moreover, SCN − forms a Li 3 N‐enriched stable SEI layer at the surface of the Li metal electrode, enhancing cycling stability. A Li‐S battery with the LiSCN electrolyte shows high current density operation (2.54 mA cm⁻ 2 ) with high discharge capacity (1133 mAh g⁻ 1 ) and prolonged cycle life (100 cycles). This work demonstrates that the cathode and anode performance in a Li‐S battery can be simply and concurrently enhanced by the single salt anion.