Pan Zeng1#, Cheng Liu1#, Xiaofeng Zhao2, Cheng Yuan1, Yungui Chen3*, Haiping Lin1*, and Liang Zhang1*
1Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials and Devices, Soochow University, Suzhou, 215123, China
2State Key Laboratory For Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China
3College of Materials Science and Engineering, Sichuan University, Chengdu 610065, China
Practical applications of lithium−sulfur (Li−S) batteries have been severely hindered by their low capacity, poor rate performance, and fast capacity degradation, which mainly originate from the notorious polysulfide shuttle effect. Herein, with density functional theory calculations, we show that the alloying of Fe into carbon-coated Co not only provides moderate binding interactions with the polysulfides to hinder their diffusion but also serves as an active catalyst in the spontaneous and successive lithiation of S8 to Li2S. Based on the fast migration of Li ions and the spontaneous lithiation of Li2S2 on the carbon-coated Fe−Co alloy, the entrapping−conversion processes of polysulfides are both thermodynamically and kinetically promoted in redox cycling. Experimentally, rationally designed Co7Fe3@porous graphite carbon−carbon nanotubes (Co7Fe3@PGC−CNT) electrocatalysts are introduced into Li−S batteries through separator functionalization. Consistent with theoretical predictions, Li−S batteries with Co7Fe3@PGC−CNT modified separators exhibit a dramatically enhanced rate capacity (788 and 631 mAh g−1 at 10 and 15 C rates, respectively) and cycling stability (a slow capacity decay of 0.05% per cycle over 1000 cycles at 2.0 C), which are superior to those of most reported Li−S batteries coupled with state-of-the-art separators. Furthermore, it is shown that the excellent hindering of the shuttle effects enables a high areal capacity of 4.7 mAh cm−2 after 90 cycles at a high sulfur loading of 6.7 mg cm−2. Our work provides a feasible method for developing high-energy and long-life Li−S batteries, which might drive the commercialization of Li−S batteries.