Within the C1s region (Fig 4a, Panel I), a variety of carbon-containing species were identified. Peaks at 284.3 eV and 284.8 eV correspond to sp 2 (C=C) and sp 3 (C-C) carbon bounds, respectively. Additional peaks at higher binding energy, such as 286.3 eV, 288.8 eV, and 290.7 eV, were assigned to C -O, carboxyl (O -C --O), and carbonates CO 3 groups. In other samples of this set, a C --O signal was also detected near 287.8 eV (Supp.7 and Supp. 9). These signals are complemented by corresponding peaks in the O1s region, with a major contribution from C -O bonds, centered at 532. Figure for all panels, illustrate the evolution of the XPS signals across all the samples of this series. During the anodic scan of the CV measurement, an increase in the intensity of signals from organic species, such as C -O is observed in both C1s and O1s regions. These signals are attributed to the decomposition products of the electrolyte and contribute to the formation of the outer layer of the CEI. Notably, the increase in these signals becomes apparent in S3, at 4.3V , coinciding with the peak of the anodic feature and subsequent potential elevation, consistent with findings reported by Kühn et al. . In contrast, during the cathodic scan, the intensity of these species decreases significantly from 4.6 V to 3.7 V. This pattern further supported by Figure . 5, exhibiting the C1s trends across all samples. The observed increase in organic species during the anodic scan is indicative of a thickening of the CEI, presumably due to electrolyte decomposition at elevated voltages, which is supported by several studies and evidenced by the reduced LiF signal from S1 to S4 (Fig. , panel IV). During discharge, the cathodic scan shows an increasing LiF signal, suggesting the reformation of LiF, along with a decrease in C -O species . At last, the XPS analysis validates the electrochemical data at every potential, pinpointing key regions within the CV profile. This correlation further enhances the integrity of our designed Auto-MISCHBARES workflow, contributing to the robustness and advancement of MAPs.