Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries

Klein, Michael J.; Goossens, Karel; Bielawski, Christopher W.; Manthiram, Arumugam

doi:10.1149/2.0051610jes

Title: 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 (Li₂S_x, 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:

Klein, Michael J. ^[1]; Goossens, Karel ^[2]; Bielawski, Christopher W. ^[3]; Manthiram, Arumugam ^[1]

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:: Fri Jul 29 00:00:00 EDT 2016

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.

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                    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

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                    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.

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@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}

}

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Works referencing / citing this record:

One‐Pot Synthesis of a Copolymer Micelle Crosslinked Binder with Multiple Lithium‐Ion Diffusion Pathways for Lithium–Sulfur Batteries
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DOI: 10.1002/cssc.201902772

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
DOI: 10.1039/c9ee01257e

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