Metal‐Halogen Interactions Inducing Phase Separation for Self‐Healing and Tough Ionogels with Tunable Thermoelectric Performance

Abstract Ionic liquid‐based thermoelectric gels become a compelling candidate for thermoelectric power generation and sensing due to their giant thermopower, good thermal stability, high flexibility, and low‐cost production. However, the materials reported to date suffer from canonical trade‐offs between self‐healing ability, stretchability, strength, and ionic conductivity. Herein, a self‐healing and tough ionogel (PEO/LiTFSI/EmimCl) with tunable thermoelectric properties by tailoring metal‐halogen bonding interactions, is developed. Different affinities between polymer matrix and salts are exploited to induce phase separation, resulting in simultaneous enhancement of ionic conductivity and mechanical strength. Molecular dynamics (MD) simulations and spectroscopic analyses show that Cl⁻ ions impair the lithium‐ether oxygen coordination, leading to changes in chain conformation. The migration difference between cations and anions is thus widened and a transition from n‐type to p‐type thermoelectric ionogels is realized. Furthermore, the dynamic interactions of metal‐ligand coordination and hydrogen bonding yield autonomously self‐healing capability, large stretchability (2000%), and environment‐friendly recyclability. Benefiting from these fascinating properties, the multifunctional PEO‐based ionogels are applied in sensors, supercapacitors, and thermoelectric power generation modules. The strategy of tuning solvation dominance to address the trade‐offs in thermoelectric ionogels and optimize their macroscopic properties offers new possibilities for the design of advanced ionogels.