Abstract
Using the grand canonical density functional theory (GC-DFT) approach, the investigation focuses on the significance of incorporating anion species into electrolyte solvation structures, particularly with doubly charged Mg2+ ions. Our work extends previous methodologies by examining the thermodynamic stability of acetonitrile (AN) at the interface with Mg3Bi2 and Mg2Sn. Based on energy comparisons, two distinct anions, TFSI− and ClO−, are strategically introduced.Despite the known chemical compatibility of alloy anodes with the electrolyte solution, our research discovers a novel form of solvent degradation, which has also been noted with pure Mg anodes and conventional electrolytes. Notably,a the AN molecule near anion species exhibits less susceptibility to reduction (-0.8 — -0.4 V vs. Mg2+/Mg) in the lower potential range, compared to the fully dissociated solvation structure.Charge density difference and density of states analyses detail how solvent molecules become electrophilic, causing the LUMO to overlap with the Fermi level at lower potentials when the electrostatic interaction with anion species is considered. Experimental studies using nuclear magnetic resonance (NMR) spectroscopy and linear sweep voltammetry (LSV) validate the theoretical outcomes, providing a comprehensive understanding. By augmenting prior approaches, our methodology offers valuable guidance for electrolyte composition based on predominant solvation structures in multivalent solutions.
Published Version
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