LAUSR

The performance of lithium metal batteries (LMBs) is determined by many factors from the bulk electrolyte to the electrode‐electrolyte interphases, which are crucially affected by electrolyte additives. Herein, the authors develop the heptafluorobutyrylimidazole (HFBMZ) as a hexa‐functional additive to inhibit the dendrite growth on the surface of lithium (Li) anode, and then improve the cycling performance and rate capabilities of Li||LiNi0.6Co0.2Mn0.2O2 (NCM622). The HFBMZ can remove the trace H2O and HF from the electrolyte, reducing the by‐products on the surface of solid electrolyte interphase (SEI) and inhibiting the dissolution of metal ions from NCM622. Also, the HFBMZ can enhance the wettability of the separator to promote uniform Li deposition. HFBMZ can make Li+ easy to be desolvated, resulting in the increase of Li+ flux on Li anode surface. Moreover, the HFBMZ can optimize the composition and structure of SEI. Therefore, the Li||Li symmetrical cells with 1 wt% HFBMZ‐contained electrolyte can achieve stable cycling for more than 1200 h at 0.5 mA cm–2. In addition, the capacity retention rate of the Li||NCM622 can reach 92% after 150 cycles at 100 mA g–1.