Solvent‐Mediated Microphase Separation in Ionogels for the Construction of Mechanically Robust and High‐Energy‐Output Moisture‐Electric Generators

ABSTRACT The rational design of mechanically robust gel‐based moisture‐electric generators (MEGs) with broad environmental adaptability is of great significance for the construction of self‐powered wearable systems, addressing critical challenges in sustainable energy harvesting for practical applications. In this study, we report a high‐energy‐output MEG based on a microphase‐separated double‐network ionogel, which contains a physically crosslinked polyvinyl alcohol network, chemically crosslinked poly(2‐acrylamido‐2‐methylpropanesulfonic acid) and hygroscopic ionic liquid (BMIMCl). The introduction of ionic liquids leads to microphase separation, resulting in the formation of a solvent‐rich phase and a polymer‐rich phase within ionogels. In this structure, the solvent‐rich phase facilitates stretching and ionic conduction, whereas the polymer‐rich phase contributes to the improvement of mechanical strength. The resultant ionogels demonstrate exceptional mechanical robustness featuring a tensile strength of 4.63 MPa, 501.02% elongation at break, 10.81 MJ m − 3 fracture toughness, and < 5% hysteresis. More importantly, benefit from the intrinsic wide‐temperature tolerance of ionic liquids, the ionogel‐based MEGs can operate over a wide humidity (30%–90% relative humidity) and temperature range (−25°C to 55°C), delivering a stabilized output voltage of 0.9–1.25 V and a record short‐circuit current density of 539.42 µA cm − 2 , outperforming most reported gel‐based MEGs. The electricity generation arises from synergistic coupling of humidity‐gradient‐driven H⁺ migration (major output current contribution) and Al electrode oxidation (major output voltage contribution). Through modular integration, 50 series‐connected units achieved an output of up to 60 V, directly powering commercial electronics, such as smartwatches and calculators. This finding provides a feasible strategy for designing all‐weather, mechanically robust, and scalable self‐powered systems.