Metal-N Coordination in Lithium-Sulfur Batteries: Inhibiting Catalyst Passivation

Xin Ao; Yang Kong; Shangquan Zhao; Zhongxin Chen; Yong Li; Xingyu Liao; Bingbing Tian

doi:10.1002/anie.202415036

Metal-N Coordination in Lithium-Sulfur Batteries: Inhibiting Catalyst Passivation

Angew Chem Int Ed Engl. 2024 Sep 21:e202415036. doi: 10.1002/anie.202415036. Online ahead of print.

Authors

Xin Ao¹, Yang Kong², Shangquan Zhao³, Zhongxin Chen⁴, Yong Li³, Xingyu Liao³, Bingbing Tian⁵

Affiliations

¹ Nanchang University, Department of Materials Science and Engineering, School of Physics and Materials Science, No. 999 Xuefu Avenue, Nanchang City, Jiangxi Province, 330031, NanChang, CHINA.
² Shenzhen University, International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, CHINA.
³ Nanchang University, Department of Materials Science and Engineering, School of Physics and Materials Science, CHINA.
⁴ The Chinese University of Hong Kong - Shenzhen, School of Science and Engineering, CHINA.
⁵ Shenzhen University, No. 3688, Nanhai Avenue, 518060, Shenzhen, CHINA.

PMID: 39305143
DOI: 10.1002/anie.202415036

Abstract

Lithium-sulfur (Li-S) batteries exhibit great potential as the next-generation energy storage techniques. Application of catalyst is widely adopted to accelerate the redox kinetics of polysulfide conversion reactions and improve battery performance. Although significant attention has been devoted to seeking new catalysts, the problem of catalyst passivation remains underexplored. Herein, we find that metal-N coordination has a previously overlooked role in preventing the catalyst passivation. In the case of nickel, the Ni catalyst reacts with S8 to produce NiSx compounds on the surface, leading to catalyst passivation and slow the kinetics of LiPSs conversion. In contrast, when Ni is coordinated with N (typically Ni-N4), S8 remains stable on the surface. The Ni-N4 exhibits excellent resistance to passivation and rapid kinetics of LiPSs conversion. Consequently, the sulfur cathode with Ni-N4 exhibits a high rate capability of 604.11 mAh g-1 at 3 C and maintains a low capacity decay rate of 0.046% per cycle over 1000 cycles at 2 C. Furthermore, preventing S passivation in M-N coordination applies not only to Ni-N4 but also to various coordination numbers and transition metals. This study reveals a new aspect of metal-N coordination in inhibiting catalyst passivation, improving our understanding of catalysts in Li-S batteries.

Keywords: catalyst passivation; lithium-sulfur batteries; metal-N coordination; molecular dynamics calculation; transition metal catalysts.