Unlike on graphite, triflate anions adsorbed on the sodium metal exhibit a strong tendency to approach the surface closely and form robust covalent bonds with the surface atoms via their oxygen atoms. These strong interfacial interactions not only enhance the stability of the resulting SEI compared to that on graphite, but also alter the arrangement of the adsorbed anions, resulting in tilted configurations. Additionally, the inherently high reactivity of the sodium surface provides an energetically favorable environment for anion decomposition during the adsorption process, resulting in an extensive formation of smaller decomposition products that strongly interact with the surface atoms. These decomposition products, which may include SO3, CF3, and CF2 groups, as well as atomic constituents like F, C, and O, tend to preferentially adsorb in hollow positions at the surface, leading to the formation of a smooth layer covering the electrode surface.