Tuning the Cathode‐Electrolyte Interphase Chemistry with Multifunctional Additive for High‐Voltage Li‐Ion Batteries

Abstract The utilization of layered oxides as cathode materials has significantly contributed to the advancement of the lithium‐ion batteries (LIBs) with high energy density and reliability. However, the structural and interfacial instability triggered by side reactions when charged to high voltage has plagued their practical applications. Here, this work reports a novel multifunctional additive, id est , 7‐Anilino‐3‐diethylamino‐6‐methyl fluoran (ADMF), which exhibits unique characteristics such as preferential adsorption, oxygen scavenging, and electropolymerization protection for high‐voltage cathodes. The ADMF demonstrates the capability to ameliorate the growth of cathode‐electrolyte interphase (CEI), effectively diminishing the dissolution of transition metal (TM) ions, reducing the interface impedance, and facilitating the Li + transport. As a result, ADMF additive with side reaction‐blocking ability significantly enhances the cycling stability of MCMB||NCM811 full‐cells at 4.4 V and MCMB||LCO full‐cells at 4.55 V, as evidenced by the 80% retention over 600 cycles and 87% retention after 750 cycles, respectively. These findings highlight the potential of the additive design strategy to modulate the CEI chemistry, representing a new paradigm with profound implications for the development of next‐generation high‐voltage LIBs.