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Title: Evaluating silicene as a potential cathode host to immobilize polysulfides in lithium–sulfur batteries

Abstract

The internal shuttle effect caused by polysulfides dissolution and migration negatively impacts lithium–sulfur battery performance. In this paper, a mesoscale simulation strategy, which involves atomistic calculation and coarse-grained molecular modeling, is employed to evaluate silicene as a potential cathode host material to immobilize polysulfides. Adsorption energies of insoluble polysulfides (Li 2S x with x =1, 2) and soluble polysulfide Li 2S 4 on pristine and doped silicene sheets are calculated. Results show that the adsorption is thermodynamically favorable and N-doped silicene is helpful in trapping intermediate discharge products, Li 2S 2 and Li 2S 4. The dissociation and reduction of long-chain polysulfides to short-chain polysulfides are observed. Electronic structure analysis shows that Li 2S x molecules interact with silicene via strong chemical bonds. The atomistic structure evolution of Li 2S layer formation on silicene is also investigated in this study. It is found that Li 2S (110) layer forms first, and then, it is converted to Li 2S (111) layer by introducing more Li 2S molecules to the substrate. Li 2S (111)/silicene interfacial structure is thermodynamically stable, and the interaction is dominated by Li–Si bonds. A coarse-grained model is developed to study and compare the growth of Li 2S onmore » silicene and graphene. Lastly, Li 2S-induced surface coverage is faster on silicene than on graphene, which indicates that a silicene-based cathode host will experience more acute surface passivation, which will adversely affect cathode performance.« less

Authors:
 [1];  [2];  [1]
  1. Texas A & M Univ., College Station, TX (United States). Dept. of Mechanical Engineering
  2. Texas A & M Univ., College Station, TX (United States). Dept. of Chemical Engineering
Publication Date:
Research Org.:
Texas A&M Engineering Experiment Station, College Station, TX (United States); Purdue Univ., West Lafayette, IN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1430275
Grant/Contract Number:  
EE0006832
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Coordination Chemistry
Additional Journal Information:
Journal Volume: 69; Journal Issue: 11-13; Journal ID: ISSN 0095-8972
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Lithium-sulfur battery; internal shuttle effect; silicene; polysulfide retention; surface passivation

Citation Formats

Liu, Zhixiao, Balbuena, Perla B., and Mukherjee, Partha P.. Evaluating silicene as a potential cathode host to immobilize polysulfides in lithium–sulfur batteries. United States: N. p., 2016. Web. doi:10.1080/00958972.2016.1184265.
Liu, Zhixiao, Balbuena, Perla B., & Mukherjee, Partha P.. Evaluating silicene as a potential cathode host to immobilize polysulfides in lithium–sulfur batteries. United States. doi:10.1080/00958972.2016.1184265.
Liu, Zhixiao, Balbuena, Perla B., and Mukherjee, Partha P.. Fri . "Evaluating silicene as a potential cathode host to immobilize polysulfides in lithium–sulfur batteries". United States. doi:10.1080/00958972.2016.1184265. https://www.osti.gov/servlets/purl/1430275.
@article{osti_1430275,
title = {Evaluating silicene as a potential cathode host to immobilize polysulfides in lithium–sulfur batteries},
author = {Liu, Zhixiao and Balbuena, Perla B. and Mukherjee, Partha P.},
abstractNote = {The internal shuttle effect caused by polysulfides dissolution and migration negatively impacts lithium–sulfur battery performance. In this paper, a mesoscale simulation strategy, which involves atomistic calculation and coarse-grained molecular modeling, is employed to evaluate silicene as a potential cathode host material to immobilize polysulfides. Adsorption energies of insoluble polysulfides (Li2Sx with x =1, 2) and soluble polysulfide Li2S4 on pristine and doped silicene sheets are calculated. Results show that the adsorption is thermodynamically favorable and N-doped silicene is helpful in trapping intermediate discharge products, Li2S2 and Li2S4. The dissociation and reduction of long-chain polysulfides to short-chain polysulfides are observed. Electronic structure analysis shows that Li2Sx molecules interact with silicene via strong chemical bonds. The atomistic structure evolution of Li2S layer formation on silicene is also investigated in this study. It is found that Li2S (110) layer forms first, and then, it is converted to Li2S (111) layer by introducing more Li2S molecules to the substrate. Li2S (111)/silicene interfacial structure is thermodynamically stable, and the interaction is dominated by Li–Si bonds. A coarse-grained model is developed to study and compare the growth of Li2S on silicene and graphene. Lastly, Li2S-induced surface coverage is faster on silicene than on graphene, which indicates that a silicene-based cathode host will experience more acute surface passivation, which will adversely affect cathode performance.},
doi = {10.1080/00958972.2016.1184265},
journal = {Journal of Coordination Chemistry},
number = 11-13,
volume = 69,
place = {United States},
year = {Fri May 27 00:00:00 EDT 2016},
month = {Fri May 27 00:00:00 EDT 2016}
}

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Cited by: 11 works
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