Ab Initio Structure Search and in Situ 7 Li NMR Studies of Discharge Products in the Li–S Battery System
Abstract
The high theoretical gravimetric capacity of the Li–S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li–S phase diagram using computational techniques and complement this with an in situ 7Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li2S, formed soon after cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li+-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li2S). Lastly, a ternary diagram is presented to rationalize the phasesmore »
- Authors:
-
- Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom
- Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48105, United States
- Theory of Condensed Matter Group, Cavendish Laboratory, University of Cambridge, J. J. Thomson Avenue, Cambridge CB3 0HE, United Kingdom
- Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom, Department of Chemistry, SUNY Stony Brook, Stony Brook, New York 11794, United States
- Publication Date:
- Research Org.:
- Stony Brook Univ., NY (United States)
- Sponsoring Org.:
- USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1171658
- Alternate Identifier(s):
- OSTI ID: 1345821
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Name: Journal of the American Chemical Society Journal Volume: 136 Journal Issue: 46; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 36 MATERIALS SCIENCE
Citation Formats
See, Kimberly A., Leskes, Michal, Griffin, John M., Britto, Sylvia, Matthews, Peter D., Emly, Alexandra, Van der Ven, Anton, Wright, Dominic S., Morris, Andrew J., Grey, Clare P., and Seshadri, Ram. Ab Initio Structure Search and in Situ 7 Li NMR Studies of Discharge Products in the Li–S Battery System. United States: N. p., 2014.
Web. doi:10.1021/ja508982p.
See, Kimberly A., Leskes, Michal, Griffin, John M., Britto, Sylvia, Matthews, Peter D., Emly, Alexandra, Van der Ven, Anton, Wright, Dominic S., Morris, Andrew J., Grey, Clare P., & Seshadri, Ram. Ab Initio Structure Search and in Situ 7 Li NMR Studies of Discharge Products in the Li–S Battery System. United States. https://doi.org/10.1021/ja508982p
See, Kimberly A., Leskes, Michal, Griffin, John M., Britto, Sylvia, Matthews, Peter D., Emly, Alexandra, Van der Ven, Anton, Wright, Dominic S., Morris, Andrew J., Grey, Clare P., and Seshadri, Ram. Mon .
"Ab Initio Structure Search and in Situ 7 Li NMR Studies of Discharge Products in the Li–S Battery System". United States. https://doi.org/10.1021/ja508982p.
@article{osti_1171658,
title = {Ab Initio Structure Search and in Situ 7 Li NMR Studies of Discharge Products in the Li–S Battery System},
author = {See, Kimberly A. and Leskes, Michal and Griffin, John M. and Britto, Sylvia and Matthews, Peter D. and Emly, Alexandra and Van der Ven, Anton and Wright, Dominic S. and Morris, Andrew J. and Grey, Clare P. and Seshadri, Ram},
abstractNote = {The high theoretical gravimetric capacity of the Li–S battery system makes it an attractive candidate for numerous energy storage applications. In practice, cell performance is plagued by low practical capacity and poor cycling. In an effort to explore the mechanism of the discharge with the goal of better understanding performance, we examine the Li–S phase diagram using computational techniques and complement this with an in situ 7Li NMR study of the cell during discharge. Both the computational and experimental studies are consistent with the suggestion that the only solid product formed in the cell is Li2S, formed soon after cell discharge is initiated. In situ NMR spectroscopy also allows the direct observation of soluble Li+-species during cell discharge; species that are known to be highly detrimental to capacity retention. We suggest that during the first discharge plateau, S is reduced to soluble polysulfide species concurrently with the formation of a solid component (Li2S) which forms near the beginning of the first plateau, in the cell configuration studied here. The NMR data suggest that the second plateau is defined by the reduction of the residual soluble species to solid product (Li2S). Lastly, a ternary diagram is presented to rationalize the phases observed with NMR during the discharge pathway and provide thermodynamic underpinnings for the shape of the discharge profile as a function of cell composition.},
doi = {10.1021/ja508982p},
journal = {Journal of the American Chemical Society},
number = 46,
volume = 136,
place = {United States},
year = {Mon Nov 10 00:00:00 EST 2014},
month = {Mon Nov 10 00:00:00 EST 2014}
}
https://doi.org/10.1021/ja508982p
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