Fluorinated Soft Chains Modulate Supramolecular Interactions Between Rigid‐Flexible Segments for High‑Performance and Two‑Component Recyclable Ionogels

Abstract Ionogels, owing to their exceptional electrochemical and environmental stability, have garnered widespread interest in flexible electronics, energy storage, and biomedicine. However, their ionic conductivity and mechanical robustness are often mutually exclusive. In this work, an ionogel (I 6 O 4 ‐IL100%) in which fluorinated soft chains regulate supramolecular interactions between rigid and flexible extended‐chain segments is presented. By rationally adjusting the ratio of rigid segments rich in hydrogen bonds to flexible segments containing polar fluorinated groups within the polyurethane matrix, and mixed with 1‐Ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide, supramolecular interactions are optimized to improve both strength and conductivity. The optimized ionogel, composed of aromatic urea and fluorinated segments, with an excellent tensile strength of 8.03 MPa ultra‐toughness of 51.67 MJ m −3 , high ionic conductivity (4.20 × 10 −4 S cm −1 ), charming transparency (93%), elasticity, water and impact resistance. Moreover, a triboelectric nanogenerator based on I 6 O 4 ‐IL100% achieves a peak power density of 2.74 W m −2 . Finally, to tackle the environmental persistence and cytotoxicity of ionic liquids, a cost‐effective recycle strategy that enables two‐component recycling of both the polymer matrix and the ionic liquid is developed. This work will open new paths for high‐performance, sustainable ionogels.