Energizing Robust Sulfur/Lithium Electrochemistry via Nanoscale-Asymmetric-Size Synergism

Sluggish redox kinetics and dendrite growth perplex the fulfillment of efficient electrochemistry in lithium–sulfur (Li–S) batteries. The complicated sulfur phase transformation and sulfur/lithium diversity kinetics necessitate an all-inclusive approach in catalyst design. Herein, a compatible mediator with nanoscale-asymmetric-size configuration by integrating Co single atoms and defective CoTe_2–x (Co_SA-CoTe_2–x@NHCF) is elaborately developed for regulating sulfur/lithium electrochemistry synchronously. Substantial electrochemistry and theoretical analyses reveal that CoTe_2–x exhibits higher catalytic activity in long-chain polysulfide transformation and Li₂S decomposition, while monodispersed Co sites are more effective in boosting sulfur reduction kinetics to regulate Li₂S deposition. Such cascade catalysis endows Co_SA-CoTe_2–x@NHCF with the all-around service of “trapping-conversion-recuperation” for sulfur species during the whole redox reaction. Furthermore, it is demonstrated by in situ transmission electron microscopy that initially formed electronic-conductive Co and ionic-conductive Li₂Te provide sufficient lithiophilic sites to regulate homogeneous Li plating and stripping with markedly suppressed dendrite growth. Consequently, by coupling the Co_SA-CoTe_2–x@NHCF interlayer and Li@Co_SA-CoTe_2–x@NHCF anode, the constructed Li–S full batteries deliver superior cycling stability and rate performance, and the flexible pouch cell exhibits stable cycling performance at 0.3 C. In conclusion, the gained insights into the synergistic effect of asymmetric-size structures pave the way for the integrated catalyst design in advanced Li–S systems.. Authors: Huang, Youzhang [State Key Laboratory of Physical Chemistry of Solid Surface, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials; Xiamen University]; Li, Jiantao [Chemical Sciences and Engineering Division; Argonne National Laboratory] (ORCID:000000032277849X); Zhang, Yinggan [State Key Laboratory of Physical Chemistry of Solid Surface, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials; Xiamen University]; Lin, Liang [State Key Laboratory of Physical Chemistry of Solid Surface, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials; Xiamen University]; Sun, Zhefei [State Key Laboratory of Physical Chemistry of Solid Surface, Fujian Key Laboratory of Surface and Interface Engineering for High Performance Materials, College of Materials; Xiamen University]. DOE Contract: AC02-06CH11357; SC0012704. Subjects: 36 MATERIALS SCIENCE