Enabling Scalable Polymer Electrolyte with Dual-Reinforced Stable Interface for 4.5 V Lithium-Metal Batteries

Hitherto, it remains a great challenge to stabilize electrolyte-electrode interfaces and impede lithium dendrite proliferation in lithium-metal batteries with high-capacity nickel-rich LiN_x Co_y Mn_{1- x-y} O₂ (NCM) layer cathodes. Herein, a special molecular-level-designed polymer electrolyte is prepared by the copolymerization of hexafluorobutyl acrylate and methylene bisacrylamide to construct dual-reinforced stable interfaces. Verified by X-ray photoelectron spectroscopy depth profiling, there are favorable solid electrolyte interphase (SEI) layers on Li metal anodes and robust cathode electrolyte interphase (CEI) on Ni-rich cathodes. The SEI enriched in lithiophilic N-(C)₃ guides the homogenous distribution of Li⁺ and facilitates the transport of Li⁺ through LiF and Li₃ N, promoting uniform Li⁺ plating and stripping. Moreover, the CEI with antioxidative amide groups can suppress the parasitic reactions between cathode and electrolyte and the structural degradation of cathode. Meanwhile, a unique two-stage rheology-tuning UV polymerization strategy is utilized, which is quite suited for continuous electrolyte fabrication with environmental friendliness. The fabricated polymer electrolyte exhibits a high ionic conductivity of 1.01 mS cm^-1 at room temperature. 4.5 V NCM622//Li batteries achieve prolonged operation with a retention rate of 85.0% after 500 cycles at 0.5 C. This work provides new insights into molecular design and processibility design for polymer-based high-voltage batteries.