Thermally Reconfigurable Interfaces Engineered by Robust Ionogels for Intelligent TENG Signal Modulation

Ionogels are promising for flexible electronics, but their use in triboelectric nanogenerators (TENGs) has been limited by weak mechanical performance and poor interfacial control. Here, we report a molecularly engineered ionogel (VP‐IL) with a “rigid–flexible combined skeleton,” featuring bicontinuous phase separation via multiple supramolecular interactions. Created by copolymerizing rigid 1‐vinylimidazole (1‐VIM) and flexible 2‐phenoxyethyl acrylate (PhEA) with ionic liquid 1‐ethyl‐3‐methylimidazolium bis(trifluoromethanesulfonyl)imide([EMIM][TFSI]) as dynamic crosslinker and phase‐separation driver, the VP‐IL ionogel exhibits a well‐defined bicontinuous phase separation orchestrated through strong cation– π anchoring of [EMIM] + onto PhEA benzene rings. The synergistic interplay of this interaction with hydrogen bonds and π – π stacking results in efficient energy dissipation and strain‐hardening in VP‐IL. Solid‐state NMR reveals the slow segmental motion activated by ionic liquids, thereby endowing the material with strong mechanical properties and charge transport capabilities. This dynamic network allows modulus switching over three orders of magnitude and rapid shape memory, supporting UV‐curable 3D printing. An intelligent TENG with a reconfigurable friction interface was developed by this material, whose output charge can be regulated on demand through micro‐patterning. This work offers a new material platform for the design of a new generation of adaptive soft robots and wearable self‐powered systems.