Effect of solvation shell structure on thermopower of liquid redox pairs

TL;DR

This study uses molecular dynamics simulations to understand how solvation shell structure affects the thermopower of redox pairs, revealing microscopic mechanisms and guiding electrolyte design for thermogalvanic batteries.

Contribution

It provides atomistic insights into solvation shell effects on thermopower, enabling targeted development of high-performance electrolytes.

Findings

Increasing acetone fraction enhances thermopower of Fe^{3+}/Fe^{2+}

Significant change in solvent dipole orientation variance correlates with thermopower

Acetone intercalates into Fe^{2+} solvation shell at high fractions

Abstract

Recent advancements in thermogalvanic batteries offer a promising route to efficient harvesting of low-grade heat with temperatures below 100 {\deg}C. The thermogalvanic temperature coefficient {\alpha}, usually referred to as effective thermopower, is the key parameter determining the power density and efficiency of thermogalvanic batteries. However, the current understanding of improving {\alpha} of redox pairs remains at the phenomenological level without microscopic insights, and the development of electrolytes with high {\alpha} largely relies on experimental trial and error. This work applies the free energy perturbation method based on molecular dynamics simulations to predict the {\alpha} of the {Fe^{3+}/Fe^{2+}} redox pair in aqueous and acetone solutions. We showed that {\alpha} of the {Fe^{3+}/Fe^{2+}} redox pair can be increased from 1.5{\pm}0.3 mV/K to 4.1{\pm}0.4 mV/K with the increased acetone to water fraction. The predicted {\alpha} of {Fe^{3+}/Fe^{2+}} both in pure water and acetone show excellent agreement with experimental values. By monitoring the fluctuation of dipole orientations in the first solvation shell, we discovered a significant change in the variance of solvent dipole orientation between Fe^{3+} and Fe^{2+}, which can be a microscopic indicator for large magnitudes of {\alpha}. The effect of acetone weight fraction in the mixed acetone-water solvent on the {\alpha} of {Fe^{3+}/Fe^{2+}} is also studied. Acetone molecules are found to intercalate into the first solvation shell of the {Fe^{2+}} ion at high acetone fractions, while this phenomenon is not observed in the solvation shell of the Fe^{3+} ion. Such solvation shell structure change of {Fe^{2+}} ions contributes to the enhanced {\alpha} at high acetone fractions. Our discovery provides atomistic insights into how solvation shell order can be leveraged to develop electrolytes with high thermopower.