Abstract

AbstractThe unstable interface between Li metal and ethylene carbonate (EC)‐based electrolytes triggers continuous side reactions and uncontrolled dendrite growth, significantly impacting the lifespan of Li metal batteries (LMBs). Herein, a bipolar polymeric protective layer (BPPL) is developed using cyanoethyl (−CH2CH2C≡N) and hydroxyl (−OH) polar groups, aiming to prevent EC‐induced corrosion and facilitating rapid, uniform Li+ ion transport. Hydrogen‐bonding interactions between −OH and EC facilitates the Li+ desolvation process and effectively traps free EC molecules, thereby eliminating parasitic reactions. Meanwhile, the −CH2CH2C≡N group anchors TFSI− anions through ion‐dipole interactions, enhancing Li+ transport and eliminating concentration polarization, ultimately suppressing the growth of Li dendrite. This BPPL enabling Li|Li cell stable cycling over 750 cycles at 10 mA cm−2 for 2 mAh cm−2. The Li|LiNi0.8Mn0.1Co0.1O2 and Li|LiFePO4 full cells display superior electrochemical performance. The BPPL provides a practical strategy to enhanced stability and performance in LMBs application.

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