Highly Stretchable, Ultra‐Soft, and Fast Self‐Healable Conductive Hydrogels Based on Polyaniline Nanoparticles for Sensitive Flexible Sensors

Abstract Herein, novel conductive composite hydrogels are developed with high stretchability, ultra‐softness, excellent conductivity, and good self‐healing ability. The hydrogels are formed in the water/glycerol binary solvent system, in which the polyaniline nanoparticles (PANI‐NPs) are incorporated into the poly(poly(ethylene glycol) methacrylate‐co‐acrylic acid) (P(PEG‐co‐AA)) scaffolds via the dynamically electrostatic interactions and hydrogen bonds. The PANI‐NPs serve as conductive fillers to assign conductivity to the hydrogel, while the enhanced interfacial interactions between the PANI‐NPs and P(PEG‐co‐AA) matrix endow the hydrogel with high stretchability (>1000%), low modulus (≈6 kPa), excellent elasticity (η = 0.07, energy loss coefficient at 500% strain), and fast self‐healing ability (93.3% after 10 mins). Particularly, the desirable anti‐freezing property is achieved by introducing a binary solvent system. The composite hydrogel‐based sensors are proposed, with the states‐independent properties, low detection limit (0.5% strain and 25 Pa), highly linear dependence, and excellent anti‐fatigue performance (>1000 cycles). In addition, during the practical wearable sensing tests, various external stimulus and human motions can be detected, including speaking, writing, joint movement, or even small water droplets, indicating the potential applications for the next generation of epidermal sensors.