Robust TiN nanoparticles polysulfide anchor for Li–S storage and diffusion pathways using first principle calculations

[Display omitted] •Facile hot-to-cold synthesis of TiN and S nanoparticles composite as cathode materials.•DFT based calculation of diffusion barrier for TiN for Li and S.•Experimental Li/S battery outstanding performances.•Short diffusion pathways, charge density distribution and charge transfer attribution. Recently, lithium–sulfur (LiS) batteries achieve incredible research interest owing to outstanding theoretical storage capacity, abundant resources, economical, and ecological affability. Nonetheless, the real usage of LS battery obstructs by shuttling-effect of soluble lithium-based polysulfides (LiPSs) that result in languid redox reactions, while the vital diffusion and migration mechanism of Li and S onto TiN surface is yet a myth. Herein, rational synthesis of titanium nitride (TiN) nanoparticles and sulfur composite (TiN-NPs@S) via dry freezing method as cathode material is explored for high efficiency LiS batteries. The ultra-small nanoparticles exhibits high surface area with narrow pores which serve as conductive channels for proficient passage for ions/electrons exchange during electrochemical energy storage reactions. The density functional theory (DFT) computational results, charge density distribution and charge transfer and analysis of geometry constructions indicate TiN surface possess stronger adsorption strength to S atom than Li atom implies TiN as polysulfide adsorbent. The TiN cathode after 100 cycles exhibits an excellent initial capacity of 1279 mAh g−1 at 0.5 C about 75.8% of theoretical capacity (1562 mAh g−1). The hot-to-cold-synthesis method projects formation of ultra-small sized nanoparticles which illuminates bright panorama for Li–S batteries to achieve excellent conductivity, high power density and energy density, which is of great advantageous for industrial applications.