We initiate our analysis by examining the adsorption characteristics of aggregated ions, the predominant ionic configuration in the NaOTF WiS electrolyte 43 . To this end, we start with a single NaOTF ion pair, which approximates 1:1 ion aggregation structures. According to Fig. , the examined ion pair demonstrates a tendency to adsorb onto both graphite and sodium surfaces, with the triflate anion adsorbing via its oxygen atoms. The calculated adsorption energies (see Fig. ) reveal a stronger and more favorable adsorption of the ion pair on the sodium surface compared to graphite. This higher adsorption propensity on sodium likely arises from chemical interactions facilitated by the inherently high reactivity of sodium metal, a topic further elaborated in subsequent discussions. Consequently, while on graphite, the adsorbed ions maintain a distance of about 3 Å from the topmost layer (Fig. ), they approach the sodium surface closely (Fig. and). Specifically, on the bcc (100) sodium lattice, the NaOTF ion pair demonstrates a strong tendency for adsorption, characterized by a high adsorption energy of -2 eV, resulting in a short vertical distance of approximately 0.8 Å between the triflate oxygen and the topmost surface layer.