Gutmann Donor Theory‐Guided Design of Mononuclear Ionic Cluster for Exceptional N‐Type Thermoelectric Ionogel

Abstract Quasi‐solid‐state, ionic liquid‐based thermogalvanic gels offer a significant solution for designing ultrasensitive ionic thermopiles due to their exceptional thermopower, superior thermal stability, and high flexibility. Constructing ternary ionogels through ionic doping‐induced ionic aggregates and modulation of ionic transport heat have been proved to be an effective strategy for achieving further enhancement of ionic thermopower. However, the theoretical basis and systematic optimization of ion‐selective doping have not been effectively verified. This study, grounded in the Gutmann donor theory for anion doping, demonstrates four universal configurations of structural reconfiguration in anion/cation clusters within ternary ionogels to progressively enhance anionic transport heat. At 80% relative humidity, this approach achieves a remarkably high negative thermopower of −25.85 mV K ⁻¹ and a high ionic conductivity of 3.21 mS cm ⁻¹ . Furthermore, this work synergistically complements the Gutmann donor anion‐doping strategy by tailoring the structure of the polyacrylate elastomer matrix and the type of cationic dopant. Ultimately, a wearable device prototype integrating 10 n‐type ion thermoelectric capacitors is demonastrated. This device yields a thermally responsive voltage of 0.774 V (ΔT = 3K), demonstrating promise for designing high‐thermopower ionic thermopiles and harvesting low‐grade thermal energy.