Bio‐Ionic Liquid‐Induced Rapid Self‐Initiating Tough Ionogels for In Situ Adhesion

ABSTRACT Synthesis of ionogels by photoinitiation and thermal initiation suffers from strict conditions and poor biocompatibility. In addition, achieving high mechanical strength and strong adhesive strength simultaneously remains difficult for ionogels. Herein, we report a bio‐ionic liquid‐induced self‐initiated strategy for the rapid and in situ polymerization mediated by liquid metal, which enables the fabrication of tough ionogels with favorable biocompatibility and robust interfacial adhesion. The malic acid/L‐(−)‐carnitine‐based ionic liquid disrupted the surface oxide layer of the liquid metal to accelerate in situ polymerization while simultaneously constructing a dynamic topological network through strong, reversible interactions with the polymer. This endowed the ionogel with high fracture strength (7.2 MPa), toughness (41.7 MJ m −3 ), and strong adhesion (7.6 MPa on glass). Ionogels exhibited photothermal responsiveness, enabling thermally reversible adhesion and real‐time adhesion states monitoring. Owing to good tissue adhesion, ionogels served as bioelectrodes for stable acquisition of physiological signals. This work offers meaningful guidance for the rational design of ionogels for applications in intelligent adhesives and bioelectronics.