Ultratough and Highly Conductive Supramolecular Poly(Vinyl Alcohol) Eutectogels via a Sequentially Enhanced Strategy

Abstract Eutectogels, composed of deep eutectic solvents (DESs) and polymeric networks, are promising as pivotal components in flexible energy storage, soft robotics, wearable electronic devices, etc. However, an inherent trade‐off between ionic conductivity and mechanical properties, which stems from the antagonism between the DES and polymeric networks, restricts the advancement of eutectogels. Herein, a sequentially enhanced strategy via freeze‐casting, solvent exchanges, and wet annealing to construct supramolecular poly(vinyl alcohol) (PVA) eutectogels with ultratough mechanical properties and high ionic conductivity is proposed. The trade‐off is reconciled by building aligned through‐pores to facilitate efficient ion transport and by further rationally regulating the aggregation structures of PVA chains to reinforce the supporting networks. Consequently, the resulting supramolecular PVA eutectogels demonstrate state‐of‐the‐art mechanical‐conductive comprehensive performances among existing eutectogels with an elongation of 3281%, a toughness of 196 MJ m−3, a fatigue threshold of 1100 J m−2, and ionic conductivity of 5.2 mS cm−1. These appealing characteristics are highly desirable for advanced soft conductors. This study will provide insights into designing next‐generation high‐performance supramolecular materials for flexible electronics is believed.