Multifunctional Filler‐Free PEDOT:PSS Hydrogels with Ultrahigh Electrical Conductivity Induced by Lewis‐Acid‐Promoted Ion Exchange

Abstract Highly conductive hydrogels with biotissue‐like mechanical properties are of great interest in the emerging field of hydrogel bioelectronics due to their good biocompatibility, deformability, and stability. Fully polymeric hydrogels may exhibit comparable Young's modulus to biotissues. However, most of these filler‐free hydrogels have a low electrical conductivity of <10 S cm⁻¹, which limits their wide applications of them in digital circuits or bioelectronic devices. In this work, a series of metal‐halides‐doped poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) hydrogels with an ultrahigh electrical conductivity up to 547 S cm⁻¹ is reported, which is 1.5 times to 10⁴ times higher than previously reported filler‐free polymeric hydrogels. Theoretical calculation demonstrated that the ion exchange between PEDOT:PSS and the metal halides played an important role to promote phase separation in the hydrogels, which thus leads to ultrahigh electrical conductivity. The high electrical conductivity resulted in multifunctional hydrogels with high performance in thermoelectrics, electromagnetic shielding, Joule heating, and sensing. Such flexible and stretchable hydrogels with ultrahigh electrical conductivity and stability upon various deformations are promising for soft bioelectronics devices and wearable electronics.