The positive reaction energies obtained in the presence of graphite (∆𝐸 ",- 536 = 0.78 𝑒𝑉 and ∆𝐸 ",- 638 = 0.13 𝑒𝑉 for the Na2OTF adsorbate, and ∆𝐸 ",- 536 = 1.6 𝑒𝑉 and ∆𝐸 ",- 638 = 1.88 𝑒𝑉 for the Na(OTF)2 adsorbate) demonstrate a lack of propensity for anion decomposition during adsorption on the graphite surface, irrespective of the aggregate structure. In contrast, the anion shows a significant propensity for decomposition during adsorption onto the sodium surface, with the anions involved in Na(OTF)2 and Na2OTF aggregates demonstrating a higher tendency for decomposition compared to that observed for a NaOTF ion pair (see Fig. , panels a and c, and Fig. , panels a-d). This underscores the pronounced tendency for anion decomposition within the ion-rich domain of a NaOTF WiS electrolyte, where numerous anions and cations participate in aggregate formations, resulting in the prevalent formation of Na(OTF)2, Na2OTF, and analogous substructures.