Pinpointing the Cl Coordination Effect on Mn-N3-Cl Moiety Toward Boosting Reaction Kinetics and Suppressing Shuttle Effect in Li-S Batteries

Yurong Yan; Ning Fu; Wei Shao; Tiantian Wang; Ying Liu; Yongsheng Niu; Yanwei Zhang; Mao Peng; Zhenglong Yang

doi:10.1002/smll.202311799

Pinpointing the Cl Coordination Effect on Mn-N₃-Cl Moiety Toward Boosting Reaction Kinetics and Suppressing Shuttle Effect in Li-S Batteries

Small. 2024 Mar 28:e2311799. doi: 10.1002/smll.202311799. Online ahead of print.

Authors

Yurong Yan¹, Ning Fu², Wei Shao¹, Tiantian Wang¹, Ying Liu², Yongsheng Niu², Yanwei Zhang², Mao Peng³, Zhenglong Yang¹

Affiliations

¹ Shanghai Key Laboratory of D & A for Metal-Functional Materials, School of Materials Science and Engineering, Tongji University, Shanghai, 200092, P. R. China.
² School of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang, 455000, P. R. China.
³ School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300350, P. R. China.

PMID: 38545998
DOI: 10.1002/smll.202311799

Abstract

Single atom catalysts (SACs) are highly favored in Li-S batteries due to their excellent performance in promoting the conversion of lithium polysulfides (LiPSs) and inhibiting their shuttling. However, the intricate and interrelated microstructures pose a challenge in deciphering the correlation between the chemical environment surrounding the active site and its catalytic activity. Here, a novel SAC featuring a distinctive Mn-N₃-Cl moiety anchored on B, N co-doped carbon nanotubes (MnN₃Cl@BNC) is synthesized. Subsequently, the selective removal of the Cl ligands while inheriting other microstructures is performed to elucidate the effect of Cl coordination on catalytic activity. The Cl coordination effectively enhances the electron cloud density of the Mn-N₃-Cl moiety, reducing the band gap and increasing the adsorption capacity and redox kinetics of LiPSs. As a modified separator for Li-S batteries, MnN₃Cl@BNC exhibits high capacities of 1384.1 and 743 mAh g^-1 at 0.1 and 3C, with a decay rate of only 0.06% per cycle over 700 cycles at 1 C, which is much better than that of MnN₃OH@BNC. This study reveals that Cl coordination positively contributes to improving the catalytic activity of the Mn-N₃-Cl moiety, providing a fresh perspective for the design of high-performance SACs.

Keywords: atomic coordination chemistry; lithium‐sulfur batteries; modified separators; single atom catalysts; ultraviolet irradiation.

Abstract

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