Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries
Abstract
The direct synthesis of Li2S2, a proposed solid intermediate in the discharge of lithium-sulfur (Li-S) batteries, was accomplished by treating elemental lithium with sulfur in liquid ammonia at -41°C. The as-synthesized product was analyzed by X-ray photoelectron spectroscopy (XPS) as well as X-ray diffraction (XRD) and determined to be a mixture of crystalline Li2S, amorphous Li2S2, and higher-order polysulfides (Li2Sx, x > 2). Monitored filtration followed by a tailored electrochemical approach was used to successfully remove the higher-order polysulfides and yielded a powder, which was determined by XPS to be comprised of ~9 mol% insoluble polysulfide species (mainly Li2S2) and ~91 mol% Li2S. Here, this material was discharged galvanostatically in an electrochemical cell and, despite the lack of soluble polysulfide species, was shown to exhibit a discharge plateau at ~2.1 V vs. Li/Li+. This result confirmed the electrochemical reducibility of electrolyte-insoluble polysulfides in Li-S batteries. Moreover, it was determined that the reduction of solid polysulfides was confined to areas where the sulfur-sulfur bonds were in intimate contact with the conductive current collector. Finally, it was observed that commercially available Li2S samples contain significant quantities of polysulfide-type impurities.
- Authors:
-
- Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program and Texas Materials Inst.
- Univ. of Texas, Austin, TX (United States). Dept. of Chemistry; Center for Multidimensional Carbon Materials, Inst. for Basic Science, Ulsan (Korea)
- Center for Multidimensional Carbon Materials, Inst. for Basic Science, Ulsan (Korea); Ulsan National Inst.of Science and Technology, Ulsan (Korea)
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1436410
- Grant/Contract Number:
- SC0005397
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the Electrochemical Society
- Additional Journal Information:
- Journal Volume: 163; Journal Issue: 9; Journal ID: ISSN 0013-4651
- Publisher:
- The Electrochemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Klein, Michael J., Goossens, Karel, Bielawski, Christopher W., and Manthiram, Arumugam. Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries. United States: N. p., 2016.
Web. doi:10.1149/2.0051610jes.
Klein, Michael J., Goossens, Karel, Bielawski, Christopher W., & Manthiram, Arumugam. Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries. United States. https://doi.org/10.1149/2.0051610jes
Klein, Michael J., Goossens, Karel, Bielawski, Christopher W., and Manthiram, Arumugam. Fri .
"Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries". United States. https://doi.org/10.1149/2.0051610jes. https://www.osti.gov/servlets/purl/1436410.
@article{osti_1436410,
title = {Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries},
author = {Klein, Michael J. and Goossens, Karel and Bielawski, Christopher W. and Manthiram, Arumugam},
abstractNote = {The direct synthesis of Li2S2, a proposed solid intermediate in the discharge of lithium-sulfur (Li-S) batteries, was accomplished by treating elemental lithium with sulfur in liquid ammonia at -41°C. The as-synthesized product was analyzed by X-ray photoelectron spectroscopy (XPS) as well as X-ray diffraction (XRD) and determined to be a mixture of crystalline Li2S, amorphous Li2S2, and higher-order polysulfides (Li2Sx, x > 2). Monitored filtration followed by a tailored electrochemical approach was used to successfully remove the higher-order polysulfides and yielded a powder, which was determined by XPS to be comprised of ~9 mol% insoluble polysulfide species (mainly Li2S2) and ~91 mol% Li2S. Here, this material was discharged galvanostatically in an electrochemical cell and, despite the lack of soluble polysulfide species, was shown to exhibit a discharge plateau at ~2.1 V vs. Li/Li+. This result confirmed the electrochemical reducibility of electrolyte-insoluble polysulfides in Li-S batteries. Moreover, it was determined that the reduction of solid polysulfides was confined to areas where the sulfur-sulfur bonds were in intimate contact with the conductive current collector. Finally, it was observed that commercially available Li2S samples contain significant quantities of polysulfide-type impurities.},
doi = {10.1149/2.0051610jes},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 163,
place = {United States},
year = {Fri Jul 29 00:00:00 EDT 2016},
month = {Fri Jul 29 00:00:00 EDT 2016}
}
Web of Science
Works referencing / citing this record:
One‐Pot Synthesis of a Copolymer Micelle Crosslinked Binder with Multiple Lithium‐Ion Diffusion Pathways for Lithium–Sulfur Batteries
journal, January 2020
- Guo, Rongnan; Zhang, Shunlong; Wang, Jianli
- ChemSusChem, Vol. 13, Issue 4
Current-density dependence of Li 2 S/Li 2 S 2 growth in lithium–sulfur batteries
journal, January 2019
- Kong, Long; Chen, Jin-Xiu; Peng, Hong-Jie
- Energy & Environmental Science, Vol. 12, Issue 10