There is currently significant interest in the development of thermoelectric generators (TEGs) that employ multi-phase fluids. While liquid TEGs show promise for harvesting waste heat or thermal energy without the limitations or material engineering associated with the Wiedemann-Franz law, the exact geometric designs of TEGs are still challenging to model, predict, and optimize, a priori. The difficulties in modeling TEG behavior may be related to the complex inter- and intra-molecular interactions that are not currently incorporated into thermodynamic model. Here we study the thermoelectric behavior with a range of molten salts or room temperature ionic liquids (RTILs) and correlate Seebeck coefficient with heat expansion. When an RTIL expands, it does work, and the voltage produced in the temperature gradient decreases. A thermodynamic two-chamber model that illustrates the measured trends associated with volumetric heat expansion is provided.
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