文献类型：期刊文献

英文题名：Engineering atomic Fe sites with asymmetrical nitrogen/sulfur coordination for stable and boosted sulfur conversion

作者：Yang, Lubin[1];Pan, Yukun[1];Shu, Qingli[1];Wang, Huimin[1];Zhang, Yongzheng[1];Ma, Cheng[2];Wang, Jitong[1];Zhang, Yayun[1,2];Qiao, Wenming[1];Ling, Licheng[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Key Lab Specially Funct Mat & Related Technol, Minist Educ, Shanghai 200237, Peoples R China

年份：2024

卷号：491

外文期刊名：CHEMICAL ENGINEERING JOURNAL

收录：;EI(收录号：20242016087736);WOS:【SCI-EXPANDED(收录号:WOS:001240869300001)】；

基金：Acknowledgements This work is supported by the National Natural Science Foundation of China (No. U21A2060, No.22178116, No.21978097) , Natural Science Foundation of Shanghai (No.22ZR1417400) , Fundamental Research Funds for the Central Universities (No. JKA01221601)

语种：英文

外文关键词：Atomic Fe sites; Asymmetrical coordination; Fe-S coordination; Electrocatalysts; Lithium-sulfur batteries

摘要：Introducing nonmetallic heteroatoms into the conventional metal-N-C configuration is thought to be an effective strategy to regulate the coordinated chemistry environment of atomic metal centers and further improve the sulfur electrochemistry behavior in lithium-sulfur batteries. Nevertheless, the modulation of heteroatoms junction states (doped or coordinated) in carbocycle is rarely explored. Herein, based on the stable pre-coordination of Fe3+ and terminal sulfhydryl/amino groups in cysteine, an asymmetrical Fe-N3S1 coordination structure in cysteine-derived graphene (Fe/CG) is rationally designed and prepared. The intervention of S atom at the first-coordination shell of Fe centers could induce the distorted spatial coordination structure, which greatly reduces the Li2S decomposition barrier. Moreover, the bonded S atom increases the d-band center (epsilon(da)) of Fe and pronouncedly activates the surrounding atoms, enhancing the electronic conductivity and reaction activity/affinity of Fe/CG, which was evidenced through theoretical calculations. The serial electro-kinetic analysis further confirms the bidirectional catalytic effect of Li2S redox conversions on Fe/CG. Consequently, the S@Fe/CG cathodes exhibit outstanding cycling stability (718.8 mAh g(-1) after 500 cycles at 1 C with a decay of 0.037 % per cycle) and rate performance (639 mAh g(-1) at 4 C). This work provides a new perspective to regulate the local chemistry environment of metal centers via coordination engineering.