Thermodynamically Guided Design of High-Entropy Organic Electrolytes

High-entropy electrolytes (HEEs) garner considerable interest for their entropy-stabilized interfacial properties, high ionic conductivity, and exceptional performance across a wide temperature range. Nevertheless, the thermodynamic evolution within these electrolytes during operation remains inadequately characterized, and the broader implications of entropy modulation in designing organic liquid electrolytes remain underexplored. This Letter delineates the thermodynamic equilibria governing organic electrolytes and elucidates how entropy dictates solvation structures and interfacial stability. We further present selection criteria for high-entropy constituents and survey recent breakthroughs in this emerging field. Additionally, we demonstrate the considerable potential of HEEs in enabling operational resilience under extreme temperature conditions. We propose that integrating thermodynamic principles into electrolyte design offers a promising avenue for understanding and tailoring ion-transport phenomena and interfacial behavior in advanced battery systems.