Acid‐Induced in Situ Phase Separation and Percolation for Constructing Bi‐Continuous Phase Hydrogel Electrodes With Motion‐Insensitive Property

Abstract Conducting polymer hydrogels have gained attention in the bioelectronics field due to their unique combination of biocompatibility and customizable mechanical properties. However, achieving both excellent conductivity and mechanical strength in a hydrogel remains a significant challenge, primarily because of the inherent conflict between the hydrophobic nature of conducting polymers and the hydrophilic characteristics of hydrogels. To address this issue, this work proposes a simple one‐step acid‐induced approach that not only promotes the gelation of hydrophilic polymers but also facilitates the in situ phase separation of hydrophobic conducting polymers under mild conditions. This results in a distinctive bi‐continuous phase structure with exceptional electrical property (906 mS cm −1 ) and mechanical performance (fracture strain of 1103%). The hydrogel forms robust percolating networks that maintain structural integrity under mechanical stress due to their entropic elasticity, providing remarkable strain insensitivity, low mechanical hysteresis, and an impressive resilience (95%). Electrodes fabricated from the conductive hydrogel exhibit stable and minimal interfacial contact impedance with skin (1–6 kilohms at 1–100 Hz) and significantly lower noise power (4.9 µV 2 ). This work believes that the motion‐insensitive characteristics and mechanical robustness of this hydrogel will enable efficient and reliable monitoring of biological signals, establishing a new benchmark in the bioelectronics.