In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

Wang, Hao; Sa, Niya; He, Meinan; Liang, Xiao; Nazar, Linda F.; Balasubramanian, Mahalingam; Gallagher, Kevin G.; Key, Baris

doi:10.1021/acs.jpcc.7b01922

In Situ NMR Observation of the Temporal Speciation of Lithium Sulfur Batteries during Electrochemical Cycling

Journal Article · Fri Mar 03 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b01922· OSTI ID:1392950

^[1]; Sa, Niya ^[1]; He, Meinan ^[2]; Liang, Xiao ^[3]; ^[3]; Balasubramanian, Mahalingam ^[4]; Gallagher, Kevin G. ^[1]; Key, Baris ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research, Chemical Sciences and Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering
Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research; Univ. of Waterloo, ON (Canada). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research, X-ray Science Division

The understanding of the reaction mechanism and temporal speciation of the lithium sulfur batteries is challenged by complex polysulfide disproportionation chemistry coupled with the precipitation and dissolution of species. In this report, for the first time, we present a comprehensive method to investigate lithium sulfur electrochemistry using in situ ⁷Li NMR spectroscopy, a technique that is capable of quantitatively capturing the evolution of the soluble and precipitated lithium (poly)sulfides during electrochemical cycling. Furthermore, through deconvolution and quantification, every lithium-bearing species was closely tracked and four-step soluble lithium polysulfide-mediated lithium sulfur electrochemistry was demonstrated in never before seen detail. Significant irreversible accumulation of Li₂S is observed on the Li metal anode after four cycles because of sulfur shuttling. We present the application of the method in order to study electrolyte/additive development and lithium protection research can be readily envisaged.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1392950

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 11 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Progress on the Critical Parameters for Lithium-Sulfur Batteries to be Practically Viable Chung, Sheng-Heng; Chang, Chi-Hao; Manthiram, Arumugam Advanced Functional Materials, Vol. 28, Issue 28 https://doi.org/10.1002/adfm.201801188	journal	May 2018
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The Progress of Li-S Batteries-Understanding of the Sulfur Redox Mechanism: Dissolved Polysulfide Ions in the Electrolytes Zheng, Dong; Wang, Gongwei; Liu, Dan Advanced Materials Technologies, Vol. 3, Issue 9 https://doi.org/10.1002/admt.201700233	journal	June 2018
Solid-State Lithium/Selenium-Sulfur Chemistry Enabled via a Robust Solid-Electrolyte Interphase Xu, Gui-Liang; Sun, Hui; Luo, Chao Advanced Energy Materials, Vol. 9, Issue 2 https://doi.org/10.1002/aenm.201802235	journal	November 2018
Deciphering the Reaction Mechanism of Lithium–Sulfur Batteries by In Situ/Operando Synchrotron‐Based Characterization Techniques Yan, Yingying; Cheng, Chen; Zhang, Liang Advanced Energy Materials, Vol. 9, Issue 18 https://doi.org/10.1002/aenm.201900148	journal	March 2019
In Situ Techniques for Developing Robust Li-S Batteries Li, Ming; Amirzadeh, Zhila; De Marco, Roland Small Methods, Vol. 2, Issue 11 https://doi.org/10.1002/smtd.201800133	journal	August 2018
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Irreversible vs Reversible Capacity Fade of Lithium-Sulfur Batteries during Cycling: The Effects of Precipitation and Shuttle Marinescu, Monica; O’Neill, Laura; Zhang, Teng Journal of The Electrochemical Society, Vol. 165, Issue 1 https://doi.org/10.1149/2.0171801jes	journal	June 2017
Polysulfide Speciation in the Bulk Electrolyte of a Lithium Sulfur Battery McBrayer, Josefine D.; Beechem, Thomas E.; Perdue, Brian R. Journal of The Electrochemical Society, Vol. 165, Issue 5 https://doi.org/10.1149/2.0441805jes	journal	January 2018
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