Boosting redox kinetics using rationally engineered cathodic interlayers comprising porous rGO–CNT framework microspheres with NiSe2-core@N-doped graphitic carbon shell nanocrystals for stable Li–S batteries

Here, we propose the synthesis of a three-dimensional (3D) nanostructure comprising NiSe2-core@N–doped graphitic carbon (NGC) shell nanocrystals securely implanted within a highly conductive and porous reduced graphene oxide–carbon nanotube (rGO–CNT) framework (3D P-NiSe2@NGC/rGO–CNT), using spray pyrolysis technique followed by selenization and utilized as multifunctional cathodic interlayers in lithium–sulfur (Li–S) cells. The uniformly distributed arrays of macropores (ϕ = 100 nm) were formed by thermal decomposition of polystyrene nanobeads (ϕ = 200 nm). The porous structure shortens the charge diffusion length, allowing rapid charge transport and efficient electrolyte percolation besides accommodating unwanted volume perturbations. The NGC shell surrounding the NiSe2 nanocrystals acted as the primary conduction conduit for electron transport, while the self-supporting rGO–CNT framework served as a secondary pathway for consecutive electron transfer besides enhancing the structural robustness. Further, the polar NiSe2 nanocrystals offered numerous chemisorption sites for effectively capturing polysulfides, thus minimizing the shuttling effect and increasing active material utilization. The Li–S cell exhibited improved rate performance (till 4.0C) and excellent cycling stability (1000cycles at 2.0C, average capacity decay rate of 0.04% per cycle). Even at severe cell parameters (effective S content = 74%, S loading = 4.5 mg cm−2, and electrolyte/sulfur = 5.7 µL mg−1), the cells delivered a stable rate performance and long-term cycling (400cycles at 0.1C, average decay rate of 0.10% per cycle). We believe the nanostructure design strategy that we developed for this study could spur the development of more enduring and practical Li–S battery technology.