Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Ong, Mitchell T.; Bhatia, Harsh; Gyulassy, Attila G.; Draeger, Erik W.; Pascucci, Valerio; Bremer, Peer -Timo; Lordi, Vincenzo; Pask, John E.

doi:10.1021/acs.jpcc.7b02006

Complex Ion Dynamics in Carbonate Lithium-Ion Battery Electrolytes

Journal Article · Mon Mar 06 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.7b02006· OSTI ID:1375301

Ong, Mitchell T. ^[1]; Bhatia, Harsh ^[1]; Gyulassy, Attila G. ^[2]; Draeger, Erik W. ^[1]; Pascucci, Valerio ^[2]; Bremer, Peer -Timo ^[1]; ^[1]; Pask, John E. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Utah, Salt Lake City, UT (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1375301

Report Number(s):: LLNL-JRNL--674755

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 12 Vol. 121; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Boosting Rechargeable Batteries R&D by Multiscale Modeling: Myth or Reality? Franco, Alejandro A.; Rucci, Alexis; Brandell, Daniel Chemical Reviews, Vol. 119, Issue 7 https://doi.org/10.1021/acs.chemrev.8b00239	journal	March 2019
Structure and dynamics in the lithium solvation shell of nonaqueous electrolytes Han, Sungho Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-42050-y	journal	April 2019
An ab initio molecular dynamics study of the solvation structure and ultrafast dynamics of lithium salts in organic carbonates: A comparison between linear and cyclic carbonates Zhang, Xiaoliu; Kuroda, Daniel G. The Journal of Chemical Physics, Vol. 150, Issue 18 https://doi.org/10.1063/1.5088820	journal	May 2019

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