Regulation of SEI Formation by Anion Receptors to Achieve Ultra‐Stable Lithium‐Metal Batteries

Despite high specific capacity (3860 mAh g⁻¹ ), the utilization of Li-metal anodes in rechargeable batteries are still hampered due to their insufficient cyclability. Herein, we report an anion-receptor-mediated carbonate electrolyte with improved performance and can ameliorate the solid electrolyte interphase (SEI) composition comparing to the blank electrolyte. It demonstrates a high average Coulombic efficiency (97.94 %) over 500 cycles in the Li/Cu cell at a capacity of 1 mAh cm⁻² . Raman spectrum and molecular modelling further clarify the screening effects of the anion receptor on the Li⁺ -PF₆ ⁻ ion coupling that results in the enhanced ion dynamics. The X-ray photoelectron spectroscopy (XPS) distinguishes the disparities in the SEI components of the developed electrolyte and the blank one, which is rationalized by the molecular insights of the Li-metal/electrolyte interface. Thus, we prepare a 2.5 Ah prototype pouch cell, exhibiting a high energy density (357 Wh kg⁻¹ ) with 90.90 % capacity retention over 50 cycles.