Irreversible vs reversible capacity fade of lithium-sulfur batteries during cycling: the effects of precipitation and shuttle
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Published version
Author(s)
Type
Journal Article
Abstract
Lithium-sulfur batteries could deliver significantly higher gravimetric energy density and lower cost than Li-ion batteries. Their mass adoption, however, depends on many factors, not least on attaining a predictive understanding of the mechanisms that determine their performance under realistic operational conditions, such as partial charge/discharge cycles. This work addresses a lack of such understanding by studying experimentally and theoretically the response to partial cycling. A lithium-sulfur model is used to analyze the mechanisms dictating the experimentally observed response to partial cycling. The zero-dimensional electrochemical model tracks the time evolution of sulfur species, accounting for two electrochemical reactions, one precipitation/dissolution reaction with nucleation, and shuttle, allowing direct access to the true cell state of charge. The experimentally observed voltage drift is predicted by the model as a result of the interplay between shuttle and the dissolution bottleneck. Other features are shown to be caused by capacity fade. We propose a model of irreversible sulfur loss associated with shuttle, such as caused by reactions on the anode. We find a reversible and an irreversible contribution to the observed capacity fade, and verify experimentally that the reversible component, caused by the dissolution bottleneck, can be recovered through slow charging. This model can be the basis for cycling parameters optimization, or for identifying degradation mechanisms relevant in applications. The model code is released as Supplementary material B.
Date Issued
2018-01-01
Date Acceptance
2017-12-03
Citation
Journal of The Electrochemical Society, 2018, 165 (1), pp.A6107-A6118
ISSN
1945-7111
Publisher
Electrochemical Society
Start Page
A6107
End Page
A6118
Journal / Book Title
Journal of The Electrochemical Society
Volume
165
Issue
1
Copyright Statement
© The Author(s) 2017. Published by ECS.
This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited.
This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited.
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/L505298/1
Subjects
Science & Technology
Physical Sciences
Technology
Electrochemistry
Materials Science, Coatings & Films
Materials Science
LI-S BATTERY
POLYSULFIDE SHUTTLE
CELLS
ELECTROLYTE
MECHANISMS
OXIDATION
VOLTAGE
0303 Macromolecular and Materials Chemistry
0306 Physical Chemistry (incl. Structural)
0912 Materials Engineering
Energy
Publication Status
Published
Date Publish Online
2017-12-30