Accelerated Conversion of Polysulfides for Ultra Long-Cycle of Li-S Battery at High-Rate over Cooperative Cathode Electrocatalyst of Ni 0.261 Co 0.739 S 2 /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 Ni x Co 1-x S 2 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 Ni Oh 2+ -S-Co Oh 2+ backbones via octahedral TM-S (TM = Ni, Co) covalency-relationship, demonstrating that fine tuning of Co Oh 2+ sites by Ni Oh 2+ substitution effectively modulates the binding energies of LiPSs on the Ni x Co 1-x S 2 @NPCTs surface. Noteworthy, the Ni 0.261 Co 0.739 S 2 @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.