Sulfur-Bridged Dual Fe–N <sub>4</sub> Sites to Boost Lithium–Sulfur Battery Performance

Despite the growing interest in d-block single-atom catalysts (SACs) for lithium-sulfur (Li-S) batteries, the localized nature of their 3d orbitals imposes a substantial energy barrier for activating sulfur intermediates during redox reactions. This limitation stems from the low mobility of electrons in 3d orbitals, which hampers effective hybridization with the 2p orbitals of lithium polysulfides (LiPS). Here, we report a single-atom iron catalyst anchored on a nitrogen-doped porous carbon scaffold, featuring a unique axial dual-layer Fe-N<sub>4</sub> structure bridged by a sulfur atom (Fe-SNC), designed to overcome these limitations. The axial configuration, stabilized by the S bridge, enables delocalization of Fe 3d orbitals and promotes dynamic electron transfer between the dual Fe-N<sub>4</sub> layers, thereby enhancing bidirectional Li-S redox kinetics. LiPS adsorption tests, density functional theory (DFT) calculations, symmetric-cell cyclic voltammetry, and potentiostatic deposition/dissolution experiments confirm the superior catalytic activity of Fe-SNC. When applied in Li-S cells, the S@Fe-SNC cathode achieves an initial capacity of 1550 mAh g<sup>-1</sup> at 0.1C and 724 mAh g<sup>-1</sup> at 3C, retaining 546 mAh g<sup>-1</sup> after 1200 cycles at 3C. Under high-sulfur-loading (7.5 mg cm<sup>-2</sup>) and lean-electrolyte conditions (<i>E</i>/<i>S</i> = 4.7 μL mg<sup>-1</sup>), it reaches excellent areal performance at 8.0 mAh cm<sup>-2</sup>. DFT results attribute the high activity to efficient interlayer electron transfer and an asymmetric dynamic spin evolution across the dual Fe-N<sub>4</sub> layers. This asymmetric spin distribution facilitates enhanced d-p orbital hybridization, particularly π-type coupling between Fe 3d<sub><i>xz</i>/yz</sub> and S 2p orbitals, thereby improving conductivity, intermediate binding strength, and overall reaction kinetics.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2025-10-16
DOI
https://doi.org/10.1021/jacs.5c14250
Citations
4
Primary Topic
Advanced Battery Materials and Technologies
Type
article
Field-Weighted Citation Impact
2.92
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article

Sulfur-Bridged Dual Fe–N 4 Sites to Boost Lithium–Sulfur Battery Performance

Jordi Arbiol, Canhuang Li, Shichang Cai, Jiachen Ma et al.
4 citations
Journal of the American Chemical Society
Advanced Battery Materials and Technologies
2.92
article

Sulfur-Bridged Dual Fe–N 4 Sites to Boost Lithium–Sulfur Battery Performance

Jordi Arbiol, Canhuang Li, Shichang Cai, Jiachen Ma, Fanglin Wu, Yuchuan Ren, Andreu Cabot, Chaoqi Zhang, Ivan Pinto‐Huguet, Xiaoyu Bi, Jiawei Zhu, Zeyan Li, Yapeng Cheng, Yao Li, Zhengxiao Guo, Jing Lü, Qian Xue, Haining Zhang, Hao Li, Jing Yu, Yanting Xie, Ren He
article en
4 citations

Abstract

Despite the growing interest in d-block single-atom catalysts (SACs) for lithium-sulfur (Li-S) batteries, the localized nature of their 3d orbitals imposes a substantial energy barrier for activating sulfur intermediates during redox reactions. This limitation stems from the low mobility of electrons in 3d orbitals, which hampers effective hybridization with the 2p orbitals of lithium polysulfides (LiPS). Here, we report a single-atom iron catalyst anchored on a nitrogen-doped porous carbon scaffold, featuring a unique axial dual-layer Fe-N<sub>4</sub> structure bridged by a sulfur atom (Fe-SNC), designed to overcome these limitations. The axial configuration, stabilized by the S bridge, enables delocalization of Fe 3d orbitals and promotes dynamic electron transfer between the dual Fe-N<sub>4</sub> layers, thereby enhancing bidirectional Li-S redox kinetics. LiPS adsorption tests, density functional theory (DFT) calculations, symmetric-cell cyclic voltammetry, and potentiostatic deposition/dissolution experiments confirm the superior catalytic activity of Fe-SNC. When applied in Li-S cells, the S@Fe-SNC cathode achieves an initial capacity of 1550 mAh g<sup>-1</sup> at 0.1C and 724 mAh g<sup>-1</sup> at 3C, retaining 546 mAh g<sup>-1</sup> after 1200 cycles at 3C. Under high-sulfur-loading (7.5 mg cm<sup>-2</sup>) and lean-electrolyte conditions (<i>E</i>/<i>S</i> = 4.7 μL mg<sup>-1</sup>), it reaches excellent areal performance at 8.0 mAh cm<sup>-2</sup>. DFT results attribute the high activity to efficient interlayer electron transfer and an asymmetric dynamic spin evolution across the dual Fe-N<sub>4</sub> layers. This asymmetric spin distribution facilitates enhanced d-p orbital hybridization, particularly π-type coupling between Fe 3d<sub><i>xz</i>/yz</sub> and S 2p orbitals, thereby improving conductivity, intermediate binding strength, and overall reaction kinetics.

Journal of the American Chemical SocietyVol. 147(43)
Institució Catalana de Recerca i Estudis Avançats (ES), United States Department of Transportation (US), Hong Kong Polytechnic University (HK), Wuhan University of Technology (CN), Peking University (CN), Chemnitz University of Technology (DE), Fuel Cells and Hydrogen (BE), Henan University of Technology (CN), Knowledge Integration (United Kingdom) (GB), Ji Hua Laboratory (CN), Institut Català de Nanociència i Nanotecnologia (ES), Institut de Recerca en Energia de Catalunya (ES), Southwest Jiaotong University (CN), Universitat de Barcelona (ES), Fuzhou University (CN), Fujian University of Technology (CN), University of Hong Kong (HK)
Openalex Percentile: Top 8%
Advanced Battery Materials and Technologies
2.92
DOISourceOpenAlex
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