High‐Performance Li‐O2 Batteries Enabled by Dibenzo‐24‐Crown‐8 Aldehyde Derivative as Electrolyte Additives

Abstract Aprotic Li‐O 2 batteries (LOB) with high theoretical energy density usually experience cathode clogging by insoluble Li 2 O 2 , along with high charge overpotential from its insulating nature. A dibenzo‐24‐crown‐8 aldehyde derivative (DB24C8A) is employed as an additive to enhance the binding strength with Li + , hence promoting the solubility of Li 2 O 2 . The generated [DB24C8A•Li + ] avoids the parasitic reactions caused by reactive O 2 − . Thus, the LOB achieves a large discharge capacity of 6939 mAh g −1 at 200 mA g −1 and a high Li 2 O 2 yield (≈93%). Moreover, DB24C8A facilitates the efficient decomposition of Li 2 O 2 via Li + coordination during the charge process, reducing the charge overpotential to 0.77 V and prolonging the lifetime of the LOB over 213 cycles at 1000 mAh g −1 and 500 mA g −1 . This work provides a novel approach to boost the performance of LOB by incorporation of crown ether‐based compounds to regulate the Li 2 O 2 growth and decomposition pathway.