Ionogels Reinforced by Ionophobic Coordination

Abstract As the key materials for next‐generation wearable and flexible electronics, ionogels are expected to combine excellent mechanical performance, efficient room‐temperature self‐healing, and facile processability. Current ionogels typically face a significant trade‐off between mechanical strength and self‐healing efficiency, limiting their practical applications. Here, “Ionophobic Coordination Reinforcement” (ICR) is introduced, a strategy that integrates ionic liquid‐phobic microphase separation with lithium‐ion coordination crosslinking. The ICR design yields a dual glass transition temperature ( T g ): −60.27 °C for maintaining soft phase mobility and 55.33 °C for reinforcing hard phase strength. This architecture achieves simultaneous high mechanical performance (6.4‐fold increase in tensile strength, 4‐fold increase in toughness, and 35.6‐fold increase in Young's modulus) and efficient self‐healing at ambient conditions. Furthermore, this dynamic supramolecular architecture also provides exceptional melt‐processability, facilitating advanced fabrication techniques such as melt spinning. Taking advantage of the high specific surface area of ionogel fibers, the sensor exhibits enhanced humidity sensitivity and rapid response to respiratory moisture changes compared to film counterparts. Integrated into a wireless platform, it enables real‐time, non‐invasive respiratory monitoring, while intrinsic self‐healing ensures long‐term stability. ICR effectively resolves the trade‐off between strength and self‐healing, offering a new paradigm for high‐performance wearable electronics, soft robotics, and adaptive sensors.