In Situ Construction of Zwitterionic Polymer Electrolytes with Synergistic Cation–Anion Regulation Functions for Lithium Metal Batteries

Abstract Here, inspired by the unique mesh geometry of fishing nets and the knotted fiber structures that can simultaneously enhance both the strength and deformability of the materials, new crosslinkers and elastic components into the polyzwitterionic electrolytes to construct high‐strength and ultra‐flexible fishing‐net‐like structure electrolytes are introduced. Specifically, the crosslinker rich in –NH can not only form chemical crosslinking points between polyzwitterion and elastic segments, but also physical crosslinking points, resulting in high strength of the electrolytes. Additionally, the elastic segments provide the electrolytes with super flexibility, strongly reducing the interface resistance of devices. Moreover, the backbone of polymers can collectively regulate anions and Li⁺, realizing stable Li⁺ deposition and suppressing the growth of lithium dendrites. As a consequence, the Li||Li symmetric cell can be stably cycled at 0.1 mA h⁻¹ for over 5500 h at 30 °C, and the assembled Li/LiFePO₄ (LFP) and Li/ LiNi_0.8Co_0.1M_0.1 (NCM 811) cells both show good cell performances at various C‐rates at 30 °C. This work provides a new perspective for the construction of polymer electrolytes with synergistic cation–anion regulation functions for high safety and high energy density solid‐state lithium batteries.