Synergistic Interaction of Dual‐Polymer Networks Containing Viologens‐Anchored Poly(ionic liquid)s Enabling Long‐Life and Large‐Area Electrochromic Organogels

Viologens-based electrochromic (EC) devices with multiple color changes, rapid response time, and simple all-in-one architecture have aroused much attention, yet suffer from poor redox stability caused by the irreversible aggregation of free radical viologens. Herein, the semi-interpenetrating dual-polymer network (DPN) organogels are introduced to improve the cycling stability of viologens-based EC devices. The primary cross-linked poly(ionic liquid)s (PILs) covalently anchored with viologens can suppress irreversible face-to-face contact between radical viologens. The secondary poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) chains with strong polar groups of -F can not only synergistically confine the viologens by the strong electrostatic effect, but also improve the mechanical performance of the organogels. Consequently, the DPN organogels show excellent cycling stability (87.5% retention after 10 000 cycles) and mechanical flexibility (strength of 3.67 MPa and elongation of 280%). Three types of alkenyl viologens are designed to obtain blue, green, and magenta colors, demonstrating the universality of the DPN strategy. Large-area EC devices (20 × 30 cm) and EC fibers based on organogels are assembled to demonstrate promising applications in green and energy-saving buildings and wearable electronics.