Post a complete discharge-charge cycle, the lithiated silicon anode maintained its integrity without any structural changes compared to its original state (Figures ) and b(II)), and the spherical particles did not pulverize, showcasing the protective role of the TzG polymer networks. However, after 400 cycles, subtle cracks due to electrode expansion became visible at lower magnifications (Figures and), which might have also arisen during the SEM sample preparation process. The S@PAN cathodes displayed minimal morphological changes after the initial cycle (Figures and) but started to form rounded aggregated particles after extensive cycling, suggesting growth and aggregation of CEI species, yet retaining excellent structural integrity even after 400 cycles. ). The XPS spectra of F1s and C1s (Figures and) for the TzG@Si anodes before cycling display typical TzG polymer bonds (Figure ), whereas post-cycling spectra illustrate a complex SEI consisting of organic ROCO 2 Li at 286.99 eV, inorganic Li 2 CO 3 at 288.8 eV, and significant amounts of LiF at 685.8 eV. The appearance of C-F bonds above 290.0 eV in the C1s spectra (Figure ) indicates the decomposition of fluoroethylene carbonate (FEC) component in the electrolyte. The peak in the C1s spectrum at 282.5 eV (Figure ) was attributable to contamination from the XPS sample holder, not from the anode material itself. Generally, the C1s and F1s spectra of the silicon anode in our full cell system showed remarkable consistency across different stages, demonstrating that the robust SEI formed effectively mitigated the decomposition of other organic solvents, thus ensuring excellent capacity retention and high Coulombic efficiency. In the case of the S@PAN cathode, discussions centered around the XPS spectra of S2p and F1s (Figure and Figure ). The S2p spectrum shown in Figure (I) reveals the sulfur characteristics of a pristine S@PAN cathode, displaying bonds such as C-S (~162 eV), S-S x (~164 eV), and weaker signals for S-N and S=N (~168 eV). Post-lithiation, the S2p spectrum of the S@PAN electrode (Figure ) showed that Li-S-S x were the predominant species within the voltage range of 0.8-3.0 V. The intensity of the S2p spectra diminished following lithiation and delithiation, indicative of CEI species coverage. As for the F1s spectra of S@PAN (Figure ), alongside the C-F bond signal at 688.3 eV from the PVDF binder and the -HCF from