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Title: Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Abstract

Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvation structure, while the counterion, PF6– undergoes more Brownian-like motion. Lastly, our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.

Authors:
 [1];  [1];  [2];  [1];  [2];  [1]; ORCiD logo [1];  [1]
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  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Utah, Salt Lake City, UT (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1375301
Report Number(s):
LLNL-JRNL-674755
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 12; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Ong, Mitchell T., Bhatia, Harsh, Gyulassy, Attila G., Draeger, Erik W., Pascucci, Valerio, Bremer, Peer -Timo, Lordi, Vincenzo, and Pask, John E. Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b02006.
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Ong, Mitchell T., Bhatia, Harsh, Gyulassy, Attila G., Draeger, Erik W., Pascucci, Valerio, Bremer, Peer -Timo, Lordi, Vincenzo, & Pask, John E. Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes. United States. https://doi.org/10.1021/acs.jpcc.7b02006
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Ong, Mitchell T., Bhatia, Harsh, Gyulassy, Attila G., Draeger, Erik W., Pascucci, Valerio, Bremer, Peer -Timo, Lordi, Vincenzo, and Pask, John E. Mon . "Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes". United States. https://doi.org/10.1021/acs.jpcc.7b02006. https://www.osti.gov/servlets/purl/1375301.
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@article{osti_1375301,
title = {Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes},
author = {Ong, Mitchell T. and Bhatia, Harsh and Gyulassy, Attila G. and Draeger, Erik W. and Pascucci, Valerio and Bremer, Peer -Timo and Lordi, Vincenzo and Pask, John E.},
abstractNote = {Li-ion battery performance is strongly influenced by ionic conductivity, which depends on the mobility of the Li ions in solution, and is related to their solvation structure. In this work, we have performed first-principles molecular dynamics (FPMD) simulations of a LiPF6 salt solvated in different Li-ion battery organic electrolytes. We employ an analytical method using relative angles from successive time intervals to characterize complex ionic motion in multiple dimensions from our FPMD simulations. We find different characteristics of ionic motion on different time scales. We find that the Li ion exhibits a strong caging effect due to its strong solvation structure, while the counterion, PF6– undergoes more Brownian-like motion. Lastly, our results show that ionic motion can be far from purely diffusive and provide a quantitative characterization of the microscopic motion of ions over different time scales.},
doi = {10.1021/acs.jpcc.7b02006},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 121,
place = {United States},
year = {Mon Mar 06 00:00:00 EST 2017},
month = {Mon Mar 06 00:00:00 EST 2017}
}
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.7b02006
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    Works referencing / citing this record:

    Structure and dynamics in the lithium solvation shell of nonaqueous electrolytes
    journal, April 2019

    Boosting Rechargeable Batteries R&D by Multiscale Modeling: Myth or Reality?
    journal, March 2019

    Structure and dynamics in the lithium solvation shell of nonaqueous electrolytes
    journal, April 2019

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