Cationic chitosan enables eutectogels with high ionic conductivity for multifunctional applications in energy harvesting and storage.

Eutectogels are popular as an emerging material in the field of flexible electronics. However, limited mechanical properties and ionic conductivity restrict their multifunctional application expansion. Herein, cationic chitosan quaternary ammonium salt (CQS) was evenly embedded into the three-dimensional porous framework of eutectogel to build ion migration channels. And a simple solvent replacement process enhanced the crystallization of polyvinyl alcohol matrix and hydrogen bonding, preparing composite eutectogels with high toughness, environmental tolerance and conductivity. The prepared gel exhibites excellent mechanical properties (1.72 MPa, 413 %) and conductivity (0.40 S·m). Under external force, three-dimensional porous network with cationic polysaccharide distribution can achieve effective piezoionic effect. Moderate CQS significantly enhances the piezoionic voltage output to 270 mV, which is 4.5 times that of the pure eutectogel. Further, the prepared composite eutectogels was used for capacitor energy storage and wearable sensing devices, and has good charge/discharge stability (94 % capacitance retention) and fast response time (292 ms). This design is typically suitable for preparing advanced multifunctional ion conductors using various natural polysaccharides with sustainable application potential.