Analyzing the S 2p spectra (Figure ) highlighted the primary reactive sites including C-S (162.3 eV, 163.5 eV), S-S x (164.2 eV, 165.4 eV), which transitioned into C-S-Li and S x -S-Li species. The S-N bonds also participated in the reactions, and deeper lithiation led to the cleavage of these Li-S-N and C-S-Li bonds, resulting in the formation of Li 2 S. Notably, Li 2 S was not detected above the cut-off voltage of 0.8 V. However, its presence was confirmed at the lower voltage of 0.2 V and was identified as amorphous through XRD analysis (Figure ). In the C1s spectra (Figure ), peaks at 285.0 eV and 286.5 eV corresponding to C-C/C=C and C-S bonds in pristine S@PAN diminished after discharging. A significant peak at 290.0 eV indicative of C-F from PVDF was observed, overlapping with a strong peak of H-C-F and Li 2 CO 3 , which increased in intensity with deeper discharging due to the decomposition of carbonate electrolytes. Additionally, the F1s spectra indicated an increase in the ratios of both LiF (685.5 eV) and Li x PF y O z (688.5 eV) as discharging progressed, suggesting a higher rate of decomposition of the FEC component and LiPF 6 in the electrolyte. The capacity performance shown in Figure reveals that, even at a deeper cut-off voltage of 0.6 V, the S@PAN-Li cells maintained high capacity and exhibited robust capacity retention. This highlights the potential for further exploration of the capabilities of the S@PAN material through the manipulation of the voltage window. and iV represent the different discharge stages of the disassembled S@PAN electrode, corresponding to the pristine state, 1.0 V, 0.8 V, and 0.2 V vs. Li + /Li, respectively.