Role of the Solvation Shell Structure and Dynamics on K-Ion and Li-Ion Transport in Mixed Carbonate Electrolytes

Ethylene and diethyl carbonates (EC : DEC) have been attractive solvents for Li-ion electrolytes because these can exhibit a good ionic conductivity and stable electrochemical performance. However, in the contemporary K-ion electrolytes, KPF6 presents a limited solubility of similar to 0.6 M in EC : DEC (volume ratio 1 : 1), which restricts its performance. Here, the molecular basis for these distinct solvation behaviors is clarified by combining experimental attenuated total reflectance-infrared spectroscopy and electrochemical impedance spectroscopy measurements with molecular dynamics simulations, revealing the distinct roles of EC and DEC solvents on the solubility, ionic conductivity, and solvation shell structures of KPF6 and LiPF6 salts in EC : DEC mixtures. In turn, these insights have enabled the formulation of a new K-ion electrolyte with EC : DEC volume ratio of 1.5 that exhibits significantly increased KPF6 solubility (similar to 0.9 M) and ionic conductivity, reaching 13.99 mS cm(-1) at 25 degrees C.

Automated summary

Experimental and simulation studies have revealed the molecular basis for the different solvation behaviors of KPF6 and LiPF6 salts in EC and DEC solvents, leading to the development of a new K-ion electrolyte with increased KPF6 solubility and enhanced ionic conductivity.