Enthalpy–Entropy Compensation Governs the Solvent-Mixing Effect in Electrochemical Thermoelectric Conversion

Thermocells convert temperature gradients into electrical energy using the entropy change of a redox reaction. The performance of thermocells is governed by the temperature coefficient of electrochemical potential (α), and the various strategies are reported to increase the α. Among the various strategies, solvent mixing has been recognized as an effective strategy; however, the underlying mechanism remains elusive due to the absence of neither systematic experimental nor reliable theoretical validation. Herein, we demonstrate that enthalpy–entropy compensation provides a general framework to model the solvent-mixing effects in thermocells. Variable-temperature electrochemistry reveals the linear relationship between hydrogen-bond entropy (ΔSHB) and enthalpy (ΔHHB) arising from the interactions between methanol and quinone dianions in acetonitrile. This enthalpy–entropy compensation principle enables the prediction of the quinone derivatives with large entropy change—and consequently large α value—through DFT-based screening of hydrogen bond enthalpy. Notably, tetramethyl-para-benzoquinone exhibits an α value of −3.1 mV K−¹, which is the highest value in the all-organic thermocells. These findings show that enthalpy–entropy compensation is a general molecular design strategy for creating high-performance thermocells.