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Title: Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode

Abstract

We report the cathode surface passivation caused by Li 2S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li 2S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li 2S film on carbon cathode surface. Li 2S film growth experiences nucleation, isolated Li 2S island growth and island coalescence. The slow adsorption rate at small S 2- concentration inhibits the formation of nucleation seeds and the lateral growth of Li 2S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li 2S nucleation seeds form in such an operating temperature range, which facilitates heterogeneous growth and thereby inhibits the lateral growth of the Li 2S film, which may also result in reduced surface passivation. Finally, the high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.

Authors:
 [1]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States). Department of Mechanical Engineering
Publication Date:
Research Org.:
Texas A&M Engineering Experiment Station, College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1430645
Grant/Contract Number:
EE0006832
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 6; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Li2S precipitation; lithium−sulfur battery; mesoscale modeling; morphology evolution; surface passivation

Citation Formats

Liu, Zhixiao, and Mukherjee, Partha P. Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode. United States: N. p., 2017. Web. doi:10.1021/acsami.6b15066.
Liu, Zhixiao, & Mukherjee, Partha P. Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode. United States. doi:10.1021/acsami.6b15066.
Liu, Zhixiao, and Mukherjee, Partha P. Mon . "Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode". United States. doi:10.1021/acsami.6b15066. https://www.osti.gov/servlets/purl/1430645.
@article{osti_1430645,
title = {Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode},
author = {Liu, Zhixiao and Mukherjee, Partha P.},
abstractNote = {We report the cathode surface passivation caused by Li2S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li2S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li2S film on carbon cathode surface. Li2S film growth experiences nucleation, isolated Li2S island growth and island coalescence. The slow adsorption rate at small S2- concentration inhibits the formation of nucleation seeds and the lateral growth of Li2S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li2S nucleation seeds form in such an operating temperature range, which facilitates heterogeneous growth and thereby inhibits the lateral growth of the Li2S film, which may also result in reduced surface passivation. Finally, the high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.},
doi = {10.1021/acsami.6b15066},
journal = {ACS Applied Materials and Interfaces},
number = 6,
volume = 9,
place = {United States},
year = {Mon Jan 23 00:00:00 EST 2017},
month = {Mon Jan 23 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 7works
Citation information provided by
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  • Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness and environmental friendliness of sulfur. However, there are still a number of challenges, such as low Coulombic efficiency and poor long-term cycling stability, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) withmore » highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li 2S 2/Li 2S) which limits the reversibility of the interfacial reactions and results in poor electrochemical performance. In conclusion, these findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.« less
  • The Li-ion cell, Li{sub 4}Ti{sub 5}O{sub 12}//PAN electrolyte//LiMn{sub 2}O{sub 4}, appears to be a classic example of a battery with passivation-free electrodes. Its gross impedance characteristics remain steady during long-term cycling at high charge/discharge rates. The cell showed excellent rechargeability at >99.9% coulombic efficiency for nearly 250 full-depth cycles, at a 1C discharge rate and a C/5 charge rate. The capacity fade was low at approximately 0.12% per cycle at around 100 cycles and {approximately}0.05% at around 200 cycles. Excellent utilizations of the cathode and anode were observed with values of 100 mAh/g of LiMn{sub 2}O{sub 4} and 140 mAh/gmore » of Li{sub 4}Ti{sub 5}O{sub 12} at 1 C discharge rate, and 70 mAh/g of LiMn{sub 2}O{sub 4} and 92 mAh/g of Li{sub 4}Ti{sub 5}O{sub 12} at 7.5C discharge rate. Electrode utilizations were significantly better under pulse discharge conditions at the 8C--16C rates. The energy density of the cell, calculated with a cell voltage of 2.6 V and practically observed cathode and anode capacities at the C/10 discharge rate, is 60 Wh/kg. The weights of the electrodes, current collectors, and electrolyte are included in this value. It is suitable for applications where high power and very long cycle life are required.« less
  • Lithium manifests a transient passivation when it is anodically polarized to approximately -2.66 NHE in LiOH electrolytes. The duration of the passivation ranges from seconds to hours. The occurrence of the passivation is independent of electrolyte concentration, flow velocity, anode--cathode contact pressure, and of the polarization technique used. The duration of the transient is proportional to electrolyte concentration; the more dilute the solution, the shorter the time. The passivation is believed due to the formation of an insulating, but unstable, aggregate of Li/sub 2/O which nucleates at active Li sites at the base of the pores in the protective LiOHmore » film. The recovery of the surface to the active state is due to the conversion of the Li/sub 2/O to LiOH in the presence of water at the Li surface. 6 figures, 1 table.« less