Operando Raman spectroscopy was employed as a vital tool to track the conversion of species and structural changes within the S@PAN matrix. The S@PAN-Li cell was discharged to 0.1 V prior to the measurements. As indicated in Figure and 5b, the observed peaks at 289 cm -1 and 366 cm -1 represent the bending of C-S bonds, while peaks at 480 cm -1 and 941 cm -1 are characteristic of S-S stretching, revealing the presence of sulfur chains (S x ) in the S@PAN composites. Additionally, two intense broad peaks at approximately 1326 cm -1 and 1552 cm -1 can be attributed to the D-band (disordered) and Gband (graphitic) respectively. The initiation of lithiation prompted the initial emergence of sulfur bond signals in the lower wavenumber range. Notably, no signals of lithium polysulfides Li 2 S x (where x = 6, 8) were detected throughout the cycling process, confirming the sulfur shuttle can be effectively mitigated by the S@PAN composite. The peaks associated with the D and G bands demonstrated a shift and a decrease in the I D /I G ratio during discharge, which, however, partially restored but with diminished intensity after recharging. This behavior suggested that the carbonized structure of the S@PAN participated in lithium-ion storage, contributing to irreversible capacity during the first cycle. Interestingly, at a discharge cut-off of 0.8 V, a peak at 800 cm -1 emerged and subsequently vanished, replaced by a new peak at 736 cm -1 not previously reported in the literature, meriting further investigation. This peak at 800 cm -1 did not reappear in the second cycle, suggesting it may correspond to an intermediate species like ethylene carbonate-Li + (EC-Li + ) or fluoroethylene carbonate-Li + (FEC-Li + ). The lowest feasible cut-off voltage was determined to be around 0.2 V, beyond which the electrode started undergoing a Li-Al alloying reaction.