The TzG@Si anode consists of silicon nanoparticles encapsulated within a porous, semiconducting polymer matrix of triazine-based graphdiyne (TzG). Growth of the polymer matrix around the silicon particles is initiated and templated directly by the copper current collector. Previous work has shown that the TzG polymer acts as a robust binder and facilitates charge transport, which enhances the electrode performance. By adjusting the TzG to silicon weight ratio to 25/75, a uniform electrode structure was formed, displaying silicon particles uniformly distributed and embedded in 2D polymer sheets (SEM, Figure and EDX, Figure ). Stability and integrity of the TzG polymer network were confirmed by Fourier-transform infrared spectra (FTIR) and Raman spectroscopy. The FTIR spectrum (Figure ) indicated a reduction in the ≡C-H (3200 to 3300 cm -1 ) stretching vibrations in the alkynyl groups post-polymerization. The Raman spectrum (Figure ) revealed characteristic bands, including diyne C≡C at 2209 cm -1 , triazine C=N at 1411 cm -1 , phenyl C=C at 1604 cm -1 , and crystalline Si-Si bonds at 518 cm -1 . The sulfurized polyacrylonitrile (S@PAN) cathode was synthesized by combining elemental sulfur powder (S 8 ) with conventional polyacrylonitrile (PAN). This process leads to the formation of a polymer where S 8 is opened and integrated as smaller sulfur molecules (S x , x = 1…4) within the polymer network. The resulting S@PAN was presented as a bulk powder (Figure ), and EDX analysis (Figure ) demonstrated an even distribution of C, N, and S atoms. Elemental analysis (Table ) showed that the sulfur content in S@PAN was approximately 40 wt%. Successful synthesis was confirmed through FTIR, Raman, and solidstate NMR (ssNMR) spectroscopy. FTIR analysis (Figure ) highlighted the disappearance of the C≡N (2247 cm-1) and C-H (2930 cm -1 ) bands, and the emergence of new S-S (513 cm -1 ), C-S (657 cm -1 ), N-S (936 cm -1 ), and C=N-C=C (1493 cm -1 , 1535 cm -1 ) bonds. Raman spectroscopy (Figure ) further clarified the sulfur chemical bonding and identified two distinct peaks corresponding to the partial carbonization of the S@PAN polymer network, the D band at 1326 cm -1 and the G band at 1552 cm -1 . The 13 C CP-MAS NMR spectrum of S@PAN (Figure ) differed from PAN, with signals at 150 ppm and 125 ppm attributed to the sp 2 hybridized conjugated carbon of C=N and C=C, respectively, indicating a slight shielding effect. X-ray diffraction (XRD) (Figure ) revealed that S@PAN is amorphous, with a broad peak corresponding to the carbon backbone of the polymer. and) SEM, FTIR, and Raman spectra of the TzG@Si anode, respectively; (e, f, and g) SEM, FTIR, and Raman spectra of the S@PAN cathode, respectively.