article · Energy storage materials · 2024
Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy
Jian Wang, Haitao Liu, Jing Zhang, Qingbo Xiao, Chong Wang, Yongzheng Zhang, Yongzheng Zhang, Meinan Liu, Qi Kang, Lujie Jia, Dong Wang, Qi Li, Wenhui Duan, Henry Adenusi, Stefano Passerini, Yuegang Zhang, Yuegang Zhang, Hongzhen Lin
Cited by 19Open access
Abstract
Understanding of interfacial Li + solvation shell structures and dynamic evolution at the electrode/electrolyte interface is requisite for developing high-energy-density Li batteries. Herein, the reorganization of Li + solvation shell at the sulfur/electrolyte interface along with the presence of a trace amount of lithium polysulfides is verified by in-situ sum frequency generation (SFG) spectroscopy together with density functional theory (DFT) calculations. Both the spectroelectrochemical and DFT calculation results reveal a strongly competitive anion adsorption of the polysulfide anion additive against the pristine electrolyte anion on the sulfur cathode surface, reorganizing the interfacial local solvation shell structure facilitating rapid Li ion transfer and conduction. Meanwhile, the evolution of the SFG signals along with the discharging/charging cycle exhibits improved reversibility, indicating the transformation of the inner Helmholtz plane layer into a stable molecular-layer polysulfide interphase rather than a dynamic diffusion layer. Consequently, applications in practical Li-S batteries reveal the capacity and cycling stability of the corresponding cells are significantly enhanced. Our work provides a methodology using in-situ SFG for probing solvation reorganization of charge carriers at electrochemical interfaces. The in-situ sum frequency generation spectroscopy together with density functional theory calculations is pioneered to get new understanding of lithium polysulfide additive in the reorganization of Li + solvation shell, modulating the inner Helmholtz plane layer into a stable molecular-layer polysulfide interphase and facilitating interfacial Li ion exhange.
Cite this paper
Wang, J., Liu, H., Zhang, J., Xiao, Q., Wang, C., Zhang, Y., Zhang, Y., Liu, M., Kang, Q., Jia, L., Wang, D., Li, Q., Duan, W., Adenusi, H., Passerini, S., Zhang, Y., Zhang, Y., & Lin, H. (2024). Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy. Energy storage materials, 67, 103289. https://doi.org/10.1016/j.ensm.2024.103289
Wang, Jian, et al. “Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy.” Energy storage materials, vol. 67, 2024, p. 103289, https://doi.org/10.1016/j.ensm.2024.103289.
Wang, Jian, Haitao Liu, Jing Zhang, Qingbo Xiao, Chong Wang, Yongzheng Zhang, Yongzheng Zhang, et al. 2024. “Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy.” Energy storage materials 67: 103289. https://doi.org/10.1016/j.ensm.2024.103289.
Wang, J. et al. (2024) ‘Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy’, Energy storage materials, 67, p. 103289. Available at: https://doi.org/10.1016/j.ensm.2024.103289.
@article{wang2024polysulfide,
title = {{Polysulfide-mediated solvation shell reorganization for fast Li+ transfer probed by in-situ sum frequency generation spectroscopy}},
author = {Wang, Jian and Liu, Haitao and Zhang, Jing and Xiao, Qingbo and Wang, Chong and Zhang, Yongzheng and Zhang, Yongzheng and Liu, Meinan and Kang, Qi and Jia, Lujie and Wang, Dong and Li, Qi and Duan, Wenhui and Adenusi, Henry and Passerini, Stefano and Zhang, Yuegang and Zhang, Yuegang and Lin, Hongzhen},
journal = {Energy storage materials},
volume = {67},
pages = {103289},
year = {2024},
doi = {10.1016/j.ensm.2024.103289}
}Made from the index record. Check names, capitalisation and page numbers against the paper. Need another style? AI for Research has over 10,000.