In situ high‐quality LiF/Li3N inorganic and phenyl‐based organic solid electrolyte interphases for advanced lithium–oxygen batteries

Lithium metal shows a great advantage as the most promising anode for its unparalleled theoretical specific capacity and extremely low electrochemical potential. However, uncontrolled lithium dendrite growth and severe side reactions of the reactive intermediates and organic electrolytes still limit the broad application of lithium metal batteries. Herein, we propose 4‐nitrobenzenesulfonyl fluoride (NBSF) as an electrolyte additive for forming a stable organic–inorganic hybrid solid electrolyte interphase (SEI) layer on the lithium surface. The abundance of lithium fluoride and lithium nitride can guarantee the SEI layer's toughness and high ionic conductivity, achieving dendrite‐free lithium deposition. Meanwhile, the phenyl group of NBSF significantly contributes to both the chemical stability of the SEI layer and the good adaptation to volume changes of the lithium anode. The lithium–oxygen batteries with NBSF exhibit prolonged cycle lives and excellent cycling stability. This simple approach is hoped to improve the development of the organic–inorganic SEI layer to stabilize the lithium anodes for lithium–oxygen batteries. Undesirable side reactions and severe lithium dendrite growth lead to premature battery death. In this work, 4‐nitrobenzenesulfonyl fluoride forms a stable organic–inorganic hybrid solid electrolyte interphase layer on the lithium surface. Benefiting from the high ionic conductivity enhanced by inorganic lithium fluoride/lithium nitride and the favorable flexibility promoted by organic phenyl‐based components, lithium–oxygen batteries achieve long‐term cycling.