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Insights into Multiphase Reactions during Self-Discharge of Li-S Batteries

  • Guobin Wen
    Guobin Wen
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    More by Guobin Wen
  • Sarish Rehman
    Sarish Rehman
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    Quantum Nano Centre, Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
  • Tom G. Tranter
    Tom G. Tranter
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    Electrochemical Innovation Lab, Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, United Kingdom
  • Debasis Ghosh
    Debasis Ghosh
    Centre for Nano & Material Sciences, JAIN University, Jain Global Campus, Bangalore 562112, India
  • Zhongwei Chen
    Zhongwei Chen
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
  • Jeff T. Gostick*
    Jeff T. Gostick
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    *Email: [email protected]
  • , and 
  • Michael A. Pope*
    Michael A. Pope
    Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    Quantum Nano Centre, Department of Chemical Engineering, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada
    *Email: [email protected]
Cite this: Chem. Mater. 2020, 32, 11, 4518–4526
Publication Date (Web):May 20, 2020
https://doi.org/10.1021/acs.chemmater.0c00235
Copyright © 2020 American Chemical Society

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    Abstract

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    Lithium-sulfur (Li-S) batteries are promising next-generation rechargeable energy storage systems due to their high energy density and use of abundant and inexpensive materials. However, rapid self-discharge and poor cycling stability due to the solubility of intermediate polysulfide conversion products have slowed their commercialization. Herein, we provide a detailed account of the multiphasic reactions occurring during the self-discharge of a Li-S battery held at various depth of discharge (DOD) through both simulation and experiment. For the first time, self-discharge of a full Li-S battery is simulated using a 1D model to describe reactions at both the anode and cathode. The model accurately describes experimentally derived results obtained over the longest durations of self-discharge studied to date (140 h). This validated model was used to follow the reversible and irreversible capacity loss caused by shuttling and precipitation of insoluble Li2S2 and Li2S as a function of DOD. While the most rapid self-discharge is observed at low DOD, this also leads to the smallest irreversible loss. The results suggest that resting a Li-S battery near 2.1 V minimizes both reversible and irreversible losses.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c00235.

    • Details model descriptions including the procedure of parameters fittings; supporting tables of stoichiometries for each species, transport properties and reference concentrations, precipitation parameters, other constant parameters, and reversible and irreversible capacity losses calculated using the eqs 1114; supporting figures of the sensitivity analyses of the formal potential potentials, exchange current densities, reference concentration, precipitation reaction rates, and chemical overpotentials; supporting figures of simulated concentration variations of PSs during one discharge–charge cycle and spatial concentration distributions of Li2S2(s) and Li2S(s); experimental voltage profiles of the interrupted discharge plot at various resting voltages and the next immediate charge, variation of specific capacity as a function of cycle number over different self-discharge periods for different cycles; and XRD patterns of various battery cell components (PDF)

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