Accelerated Conversion of Polysulfides for Ultra Long-Cycle of Li-S Battery at High-Rate over Cooperative Cathode Electrocatalyst of Ni0.261Co0.739S2/N-Doped CNTs.

Despite the very high theoretical energy density, Li-S batteries still need to fundamentally overcome the sluggish redox kinetics of lithium polysulfides (LiPSs) and low sulfur utilization that limit the practical applications. Here, highly active and stable cathode, nitrogen-doped porous carbon nanotubes (NPCTs) decorated with NixCo1-xS2 nanocrystals are systematically synthesized as multi-functional electrocatalytic materials. The nitrogen-doped carbon matrix can contribute to the adsorption of LiPSs on heteroatom active sites with buffering space. Also, both experimental and computation-based theoretical analyses validate the electrocatalytic principles of co-operational facilitated redox reaction dominated by covalent-site-dependent mechanism; the favorable adsorption-interaction and electrocatalytic conversion of LiPSs take place subsequently by weakening sulfur-bond strength on the catalytic NiOh 2+-S-CoOh 2+ backbones via octahedral TM-S (TM = Ni, Co) covalency-relationship, demonstrating that fine tuning of CoOh 2+ sites by NiOh 2+ substitution effectively modulates the binding energies of LiPSs on the NixCo1-xS2@NPCTs surface. Noteworthy, the Ni0.261Co0.739S2@NPCTs catalyst shows great cyclic stability with a capacity of up to 511 mAh g-1 and only 0.055% decay per cycle at 5.0 C during 1000 cycles together with a high areal capacity of 2.20 mAh cm-2 under 4.61 mg cm-2 sulfur loading even after 200 cycles at 0.2 C. This strategy highlights a new perspective for achieving high-energy-density Li-S batteries.