Role of Heat Expansion with a Series of Ionic Liquids: The Case for Isochoric Thermoelectric Generators and Minimal Steric Repulsion

The role of convection in liquid thermoelectric cells may be difficult to predict because the inter- and intra-molecular interactions are not currently incorporated into thermodynamic models. Here, we study the thermoelectric response of a series of five anhydrous 1-methyl-3-alkylimidazolium halide ionic liquids with varied chain length and counterion in a high-aspect-ratio, horizontal-temperature-gradient geometry, where convection is minimal. While a canonical, constant-volume thermodynamic model indicates that greater disparity and longer aliphatic groups should exhibit larger Seebeck coefficients, we instead measure the opposite: Longer aliphatic chains correlate with lower densities and greater heat expansion, stronger intermolecular associations, stronger steric repulsion, and lower Seebeck coefficients. As evidence of the critical role of thermal expansion, we measure that the Seebeck effect is nonlinear: Values of −2.8 mV/K with a 10 K temperature difference and −1.8 mV/K with a 50 K difference are measured with ether ion. Our results indicate that steric repulsion and heat expansion are important considerations in ionic liquid design; with large temperature differences, the Seebeck coefficient correlates negatively with heat expansion. Our results suggest that Seebeck values may improve if thermal expansion and steric forces are limited in a pressurized, isochoric, convection-free design.