High Areal Capacity and Sustainable High Energy in Ferroelectric Doped Holey Graphene/Sulfur Composite Cathode for Lithium-Sulfur Batteries

In this study, we are reporting the impact of the incorporation of ferroelectric nanoparticles (FNPs), such as BaTiO₃ (BTO), BiFeO₃ (BFO), Bi₄NdTi₃Fe_0.7Ni_0.3O₁₅ (BNTFN), and Bi₄NdTi₃Fe_0.5Co_0.5O₁₅ (BNTFC), as well as the mass loading of sulfur to fabricated solvent-free sulfur/holey graphene-carbon black/polyvinylidene fluoride (S/FNPs/CBhG/PVDF) composite electrodes to achieve high areal capacity for lithium-sulfur (Li-S) batteries. The dry-press method was adopted to fabricate composite cathodes. The hG, a conductive and lightweight scaffold derived from graphene, served as a matrix to host sulfur and FNPs for the fabrication of solvent-free composites. Raman spectra confirmed the dominant hG framework for all the composites, with strong D, G, and 2D bands. The surface morphology of the fabricated cathode system showed a homogeneous distribution of FNPs throughout the composites, confirmed by the EDAX spectra. The observed Li⁺ ion diffusion coefficient for the composite cathode started at 2.17 × 10⁻¹⁶ cm²/s (S₂₅(CBhG)₆₅PVDF₁₀) and reached up to the highest value (4.15 × 10⁻¹⁵ cm²/s) for S₂₅BNTFC₅(CBhG)₆₀PVDF₁₀. The best discharge capacity values for the S₂₅(CBhG)₆₅PVDF₁₀ and S₂₅BNTFC₅(CBhG)₆₀PVDF₁₀ composites started at 1123 mAh/g_s and 1509 mAh/g_s and dropped to 612 mAh/g_s and 572 mAh/g_s, respectively, after 100 cycles; similar behavior was exhibited by the other composites that were among the best. These are better values than those previously reported in the literature. The incorporation of ferroelectric nanoparticles in the cathodes of Li-S batteries reduced the rapid formation of polysulfides due to their internal electric fields. The areal capacity for the S₂₅(CBhG)₆₅PVDF₁₀ composites was 4.84 mAh/cm² with a mass loading of 4.31 mg_s/cm², while that for the S₂₅BNTFC₅(CBhG)₆₀PVDF₁₀ composites was 6.74 mAh/cm² with a mass loading of 4.46 mg_s/cm². It was confirmed that effective FNP incorporation within the S cathode improves the cycling response and stability of cathodes, enabling the high performance of Li-S batteries.