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

Title: 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)

Cite

Export

Save

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

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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1392950

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 35 works

Citation information provided by
Web of Science

References (27)

Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Critical Link between Materials Chemistry and Cell-Level Design for High Energy Density and Low Cost Lithium-Sulfur Transportation Battery Eroglu, Damla; Zavadil, Kevin R.; Gallagher, Kevin G. Journal of The Electrochemical Society, Vol. 162, Issue 6 https://doi.org/10.1149/2.0611506jes	journal	January 2015
Lithium−Air Battery: Promise and Challenges Girishkumar, G.; McCloskey, B.; Luntz, A. C. The Journal of Physical Chemistry Letters, Vol. 1, Issue 14 https://doi.org/10.1021/jz1005384	journal	June 2010
Lithium-Sulfur Cells: The Gap between the State-of-the-Art and the Requirements for High Energy Battery Cells Hagen, Markus; Hanselmann, Dominik; Ahlbrecht, Katharina Advanced Energy Materials, Vol. 5, Issue 16, 1401986 https://doi.org/10.1002/aenm.201401986	journal	April 2015
Erratum: Li–O2 and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 2 https://doi.org/10.1038/nmat3237	journal	December 2011
Challenges and Prospects of Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Su, Yu-Sheng Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300179v	journal	June 2012
New Approaches for High Energy Density Lithium–Sulfur Battery Cathodes Evers, Scott; Nazar, Linda F. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar3001348	journal	June 2012
A High Energy Lithium-Sulfur Battery with Ultrahigh-Loading Lithium Polysulfide Cathode and its Failure Mechanism Qie, Long; Zu, Chenxi; Manthiram, Arumugam Advanced Energy Materials, Vol. 6, Issue 7 https://doi.org/10.1002/aenm.201502459	journal	February 2016
Polysulfide shuttle control: Towards a lithium-sulfur battery with superior capacity performance up to 1000 cycles by matching the sulfur/electrolyte loading Cheng, Xin-Bing; Huang, Jia-Qi; Peng, Hong-Jie Journal of Power Sources, Vol. 253 https://doi.org/10.1016/j.jpowsour.2013.12.031	journal	May 2014
Lithium–sulfur batteries: Influence of C-rate, amount of electrolyte and sulfur loading on cycle performance Brückner, Jan; Thieme, Sören; Grossmann, Hannah Tamara Journal of Power Sources, Vol. 268 https://doi.org/10.1016/j.jpowsour.2014.05.143	journal	December 2014
Polysulfide Shuttle Study in the Li/S Battery System Mikhaylik, Yuriy V.; Akridge, James R. Journal of The Electrochemical Society, Vol. 151, Issue 11, p. A1969-A1976 https://doi.org/10.1149/1.1806394	journal	January 2004
On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries Aurbach, Doron; Pollak, Elad; Elazari, Ran Journal of The Electrochemical Society, Vol. 156, Issue 8, p. A694-A702 https://doi.org/10.1149/1.3148721	journal	January 2009
A new approach to improve cycle performance of rechargeable lithium–sulfur batteries by inserting a free-standing MWCNT interlayer Su, Yu-Sheng; Manthiram, Arumugam Chemical Communications, Vol. 48, Issue 70, p. 8817-8819 https://doi.org/10.1039/c2cc33945e	journal	January 2012
A Graphene-Pure-Sulfur Sandwich Structure for Ultrafast, Long-Life Lithium-Sulfur Batteries Zhou, Guangmin; Pei, Songfeng; Li, Lu Advanced Materials, Vol. 26, Issue 4 https://doi.org/10.1002/adma.201302877	journal	November 2013
A Soft Approach to Encapsulate Sulfur: Polyaniline Nanotubes for Lithium-Sulfur Batteries with Long Cycle Life Xiao, Lifen; Cao, Yuliang; Xiao, Jie Advanced Materials, Vol. 24, Issue 9, p. 1176-1181 https://doi.org/10.1002/adma.201103392	journal	January 2012
Polysulfide dissolution control: the common ion effect Shin, Eon Sung; Kim, Keon; Oh, Si Hyoung Chem. Commun., Vol. 49, Issue 20 https://doi.org/10.1039/C2CC36986A	journal	January 2013
Sulfur-Impregnated Activated Carbon Fiber Cloth as a Binder-Free Cathode for Rechargeable Li-S Batteries Elazari, Ran; Salitra, Gregory; Garsuch, Arnd Advanced Materials, Vol. 23, Issue 47, p. 5641-5644 https://doi.org/10.1002/adma.201103274	journal	November 2011
In-situ X-ray diffraction studies of lithium–sulfur batteries Cañas, Natalia A.; Wolf, Steffen; Wagner, Norbert Journal of Power Sources, Vol. 226 https://doi.org/10.1016/j.jpowsour.2012.10.092	journal	March 2013
Effects of Liquid Electrolytes on the Charge–Discharge Performance of Rechargeable Lithium/Sulfur Batteries: Electrochemical and in-Situ X-ray Absorption Spectroscopic Studies Gao, Jie; Lowe, Michael A.; Kiya, Yasuyuki The Journal of Physical Chemistry C, Vol. 115, Issue 50, p. 25132-25137 https://doi.org/10.1021/jp207714c	journal	October 2011
New insight into the working mechanism of lithium–sulfur batteries: in situ and operando X-ray diffraction characterization Waluś, Sylwia; Barchasz, Céline; Colin, Jean-François Chemical Communications, Vol. 49, Issue 72 https://doi.org/10.1039/c3cc43766c	journal	January 2013
Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott The Journal of Physical Chemistry Letters, Vol. 4, Issue 19 https://doi.org/10.1021/jz401763d	journal	September 2013
Lithium/Sulfur Cell Discharge Mechanism: An Original Approach for Intermediate Species Identification Barchasz, Céline; Molton, Florian; Duboc, Carole Analytical Chemistry, Vol. 84, Issue 9 https://doi.org/10.1021/ac2032244	journal	April 2012
Solvent-Dictated Lithium Sulfur Redox Reactions: An Operando UV–vis Spectroscopic Study Zou, Qingli; Lu, Yi-Chun The Journal of Physical Chemistry Letters, Vol. 7, Issue 8 https://doi.org/10.1021/acs.jpclett.6b00228	journal	April 2016
Ab Initio Structure Search and in Situ ⁷ Li NMR Studies of Discharge Products in the Li–S Battery System See, Kimberly A.; Leskes, Michal; Griffin, John M. Journal of the American Chemical Society, Vol. 136, Issue 46 https://doi.org/10.1021/ja508982p	journal	November 2014
Following the Transient Reactions in Lithium–Sulfur Batteries Using an In Situ Nuclear Magnetic Resonance Technique Xiao, Jie; Hu, Jian Zhi; Chen, Honghao Nano Letters, Vol. 15, Issue 5 https://doi.org/10.1021/acs.nanolett.5b00521	journal	April 2015
Tailoring Porosity in Carbon Nanospheres for Lithium–Sulfur Battery Cathodes He, Guang; Evers, Scott; Liang, Xiao ACS Nano, Vol. 7, Issue 12 https://doi.org/10.1021/nn404439r	journal	November 2013
In situ NMR observation of the formation of metallic lithium microstructures in lithium batteries Bhattacharyya, Rangeet; Key, Baris; Chen, Hailong Nature Materials, Vol. 9, Issue 6 https://doi.org/10.1038/nmat2764	journal	May 2010

Cited By (9)

Self-Discharge Behavior of Lithium-Sulfur Batteries at Different Electrolyte/Sulfur Ratios Shen, Chao; Xie, Jianxin; Zhang, Mei Journal of The Electrochemical Society, Vol. 166, Issue 3 https://doi.org/10.1149/2.0461903jes	journal	January 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
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
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
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
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
A Comprehensive Understanding of Lithium–Sulfur Battery Technology Li, Tao; Bai, Xue; Gulzar, Umair Advanced Functional Materials, Vol. 29, Issue 32 https://doi.org/10.1002/adfm.201901730	journal	June 2019
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
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

Similar Records

Controlling the polysulfide diffusion in lithium-sulfur batteries with a polymer membrane with intrinsic nanoporosity

Journal Article · Mon Jan 08 00:00:00 EST 2018 · Materials Today Energy · OSTI ID:1392950

Yu, Xingwen; Feng, Sinan; Boyer, Mathew J.; +7 more

Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries

Journal Article · Thu May 25 00:00:00 EDT 2017 · ACS Central Science · OSTI ID:1392950

Lee, Chang-Wook; Pang, Quan; Ha, Seungbum; +6 more

Palladium nanocrystals-imbedded mesoporous hollow carbon spheres with enhanced electrochemical kinetics for high performance lithium sulfur batteries

Journal Article · Fri Nov 30 00:00:00 EST 2018 · Carbon · OSTI ID:1392950

Ma, Shaobo; Wang, Liguang; Wang, Yang; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
25 ENERGY STORAGE

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

Citation Formats

References (27)

Cited By (9)

Similar Records

Related Subjects