Visualizing interfacial collective reaction behaviour of Li–S batteries

Zhou, Shiyuan; Shi, Jie; Liu, Sangui; Li, Gen; Pei, Fei; Chen, Youhu; Deng, Junxian; Zheng, Qizheng; Li, Jiayi; Zhao, Chen; Hwang, Inhui; Sun, Cheng-Jun; Liu, Yuzi; Deng, Yu; Huang, Ling; Qiao, Yu; Xu, Gui-Liang; Chen, Jian-Feng; Amine, Khalil; Sun, Shi-Gang; Liao, Hong-Gang

doi:10.1038/s41586-023-06326-8

Title: Visualizing interfacial collective reaction behaviour of Li–S batteries

Journal Article · 05 September 2023 · Nature (London)

DOI: https://doi.org/10.1038/s41586-023-06326-8 · OSTI ID:2427973

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Xiamen University (China)
Beijing University of Chemical Technology (China)
Nanjing Univ. (China)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States). Center for Nanoscale Materials (CNM)
Xiamen University (China); Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen (China)

Benefiting from high energy density (2,600 Wh kg^-1)) and low cost, lithium-sulfur (Li-S) batteries are considered promising candidates for advanced energy-storage systems. Despite tremendous efforts in suppressing the long-standing shuttle effect of lithium polysulfides, understanding of the interfacial reactions of lithium polysulfides at the nanoscale remains elusive. This is mainly because of the limitations of in situ characterization tools in tracing the liquid-solid conversion of unstable lithium polysulfides at high temporal-spatial resolution. There is an urgent need to understand the coupled phenomena inside Li-S batteries, specifically, the dynamic distribution, aggregation, deposition and dissolution of lithium polysulfides. Here, by using in situ liquid-cell electrochemical transmission electron microscopy, we directly visualized the transformation of lithium polysulfides over electrode surfaces at the atomic scale. Notably, an unexpected gathering-induced collective charge transfer of lithium polysulfides was captured on the nanocluster active-centre-immobilized surface. It further induced an instantaneous deposition of nonequilibrium Li2S nanocrystals from the dense liquid phase of lithium polysulfides. Without mediation of active centres, the reactions followed a classical single-molecule pathway, lithium polysulfides transforming into Li₂S₂ and Li₂S step by step. Molecular dynamics simulations indicated that the long-range electrostatic interaction between active centres and lithium polysulfides promoted the formation of a dense phase consisting of Li⁺ and S_n^2- (2 < n ≤ 6), and the collective charge transfer in the dense phase was further verified by ab initio molecular dynamics simulations. Finally, the collective interfacial reaction pathway unveils a new transformation mechanism and deepens the fundamental understanding of Li-S batteries.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Fundamental Research Funds for the Central Universities; National Natural Science Foundation of China (NSFC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2427973

Journal Information:: Nature (London), Journal Name: Nature (London) Journal Issue: 7977 Vol. 621; ISSN 0028-0836

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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