Coupling multifunctional catalytic active sites into metal carbide catalysts to promote the multipath bidirectional conversion of Li-S redox

Li-S batteries are hampered by sluggish liquid-solid redox and shuttle effects. Herein, a strategy of coupling multifunctional catalytic sites is proposed to fabricate bidirectional catalysts to promote multipath bidir-ectional Li-S redox conversion. By engineering Co or Zr dopants into Ni3C/C, the obtained Co0.30Ni2.70C/C and Zr0.30Ni2.70C/C electrocatalysts play different roles in polysulfide adsorption and multipath bidirectional conversion. During the discharging/charging process, due to limited electron transfer between the Co3+/Co2+ pair and polysulfides, Co sites themselves are catalytically inactive for the conversion of polysulfides and only act as promoters to improve the catalytic activity of Ni sites. In contrast, in addition to being promoters, Zr sites serve as electron acceptors and donors to catalyze bidirectional Li-S redox due to the flexible electron transfer between the Zr4+/Zr2+ pair and polysulfides. Such bidirectional electron transfer is ac-companied by thiosulfate-mediated redox. Therefore, Zr doping not only accelerates the inherent solid (S8) -liquid (polysulfide)-solid (Li2S) conversion pathway but also propels the reversible thiosulfate-mediated conversion pathway. As a result, when the Zr0.30Ni2.70C/C nanosheets were used to modify the commercial PP separator, the Li-S batteries exhibit improved electrochemical performance (a decay of 0.0756 % over 200 cycles with a sulfur loading of 5.0 mgs cm-2).(c) 2022 Elsevier B.V. All rights reserved.