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Ab Initio Structure Search and in Situ ^7Li NMR Studies of Discharge Products in the Li–S Battery System

See, Kimberly A. and Leskes, Michael and Griffin, John M. and Britto, Sylvia and Matthews, Peter D. and Emly, Alexander and Van der Ven, Anton and Wright, Dominic S. and Morris, Andrew J. and Grey, Clare P. and Seshadri, Ram (2014) Ab Initio Structure Search and in Situ ^7Li NMR Studies of Discharge Products in the Li–S Battery System. Journal of the American Chemical Society, 136 (46). pp. 16368-16377. ISSN 0002-7863. PMCID PMC4353022. doi:10.1021/ja508982p.

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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 Li_2S, 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 (Li_2S) 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 (Li_2S). 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.

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See, Kimberly A.0000-0002-0133-9693
Alternate Title:Ab Initio Structure Search and in Situ 7Li NMR Studies of Discharge Products in the Li–S Battery System
Additional Information:© 2014 American Chemical Society. ACS AuthorChoice - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. Received: August 31, 2014. Published: November 10, 2014. The authors would like to thank Dr. Jerry Hu for assistance on solution NMR experiments and Maxwell J. Robb for helpful discussions. Fellowship support to K.A.S. from the ConvEne IGERT Program of the National Science Foundation (DGE 0801627) is gratefully acknowledged. A.J.M. acknowledges the support from the Winton Programme for the Physics of Sustainability. P.D.M. and D.S.W. thank the UK-EPSRC for financial support. This research made use of the shared experimental facilities of the Materials Research Laboratory (MRL), supported by the MRSEC Program of the NSF under award no. DMR 1121053. The MRL is a member of the NSF-funded Materials Research Facilities Network ( C.P.G. and M.L. thank the U.S. DOE Office of Vehicle Technologies (contract no. DE-AC02-05CH11231) and the EU ERC (via an Advanced Fellowship to C.P.G.) for funding. The authors declare no competing financial interest.
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-0801627
Winton Programme for the Physics of SustainabilityUNSPECIFIED
Engineering and Physical Sciences Research Council (EPSRC)UNSPECIFIED
Department of Energy (DOE)DE-AC02-05CH11231
European Research Council (ERC)UNSPECIFIED
Issue or Number:46
PubMed Central ID:PMC4353022
Record Number:CaltechAUTHORS:20180607-131745759
Persistent URL:
Official Citation:Ab Initio Structure Search and in Situ 7Li NMR Studies of Discharge Products in the Li–S Battery System Kimberly A. See, Michal Leskes, John M. Griffin, Sylvia Britto, Peter D. Matthews, Alexandra Emly, Anton Van der Ven, Dominic S. Wright, Andrew J. Morris, Clare P. Grey, and Ram Seshadri Journal of the American Chemical Society 2014 136 (46), 16368-16377 DOI: 10.1021/ja508982p
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86890
Deposited By: George Porter
Deposited On:07 Jun 2018 20:30
Last Modified:15 Nov 2021 20:43

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