Redistribution of d-orbital in Fe-N4 active sites optimizing redox kinetics of the sulfur cathode

被引：54
作者：
Cao, Guiqiang [1 ,2 ]
Li, Xifei [1 ,2 ]
Duan, Ruixian [1 ,2 ]
Xu, Kaihua [3 ]
Zhang, Kun [3 ]
Chen, Liping [4 ]
Jiang, Qinting [1 ,2 ]
Li, Jun [1 ,2 ]
Wang, Jingjing [1 ,2 ]
Li, Ming [1 ,2 ]
Wang, Ni [1 ,2 ]
Wang, Jing [1 ,2 ]
Xi, Yukun [1 ,2 ]
Xie, Chong [1 ,2 ]
Li, Wenbin [1 ,2 ]
机构：
[1] Xian Univ Technol, Inst Adv Electrochem Energy, Sch Mat Sci & Engn, Xian 710048, Peoples R China
[2] Minist Educ, Engn Res Ctr Conducting Mat & Composite Technol, Shaanxi, Peoples R China
[3] GEM Co Ltd, Shenzhen 518101, Peoples R China
[4] Xian Univ Architecture & Technol, Shaanxi Key Lab Nanomat & Nanotechnol, Xian 710055, Peoples R China
来源：
NANO ENERGY | 2023年 / 116卷
基金：
中国国家自然科学基金;
关键词：
Sulfur cathode; Redox kinetics; Single Fe atom catalysts; Coordination configuration; Modulating d-orbital; POROUS CARBON; CONVERSION; IRON; NANOPARTICLES; DESIGN;
D O I：
10.1016/j.nanoen.2023.108755
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
Redistributing the d-orbital of single Fe atom catalysts (SFeACs) has been challenging to optimize redox kinetics of lithium sulfur batteries (LSBs). Here, the Fe-N4/S2C with mounting energy level of dz2 and partial occupation of dxz is controllably fabricated. The increased dz2, originating from thiophene sulfur, upshifts d band center compared to the Fe-N4/C with planar symmetric structure. That promotes electron transfer between Fe-N4 and sulfur, enhancing conversion of polysulfides and solid products. The lower fill of dxz develops hybridization between Fe and S atoms via the form of bonding and antibonding, with alleviating the loss of sulfur. Thus, the sulfur cathode with Fe-N4/S2C delivers a high capacity of 749 mAh g-1 at 2.0 C, accompanied by excellent stability with a lower capacity decay of 0.07% per cycle. This work has developed a novel coordination configuration towards SFeACs and uncovered the intrinsic mechanism of facilitated redox kinetics with SFeACs for LSBs.
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页数：11
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