Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

Yadong He; Rui Qiao; Jenel Vatamanu; Oleg Borodin; Dmitry Bedrov; Jingsong Huang; Bobby G. Sumpter

doi:10.1021/acs.jpclett.5b02378

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

Yadong He, Rui Qiao, Jenel Vatamanu, Oleg Borodin, Dmitry Bedrov, Jingsong Huang, Bobby G. Sumpter

Research output: Contribution to journal › Article › peer-review

78 Scopus citations

Abstract

Molecular simulations of the diffusion of EMIM⁺ and TFSI^- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching 5 × 10^-9 m²/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

Original language	English
Pages (from-to)	36-42
Number of pages	7
Journal	Journal of Physical Chemistry Letters
Volume	7
Issue number	1
DOIs	https://doi.org/10.1021/acs.jpclett.5b02378
State	Published - Jan 7 2016

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

Funding

We thank the Clemson-CCIT and ARC at Virginia Tech for generous allocations of computer time on the Palmetto cluster and BlueRidge cluster. R.Q. acknowledges the support from NSF (CBET-1461842). R.Q. was partially supported by an appointment to the HERE program for faculty at the Oak Ridge National Laboratory (ORNL) administered by ORISE. D.B. and J.V. acknowledge the University of Utah MRSEC (NSF grant no. DMR 11-21252) for the support through the seed grant program. J.H. and B.G.S. acknowledge work performed at the Center for Nanophase Materials Sciences, a U.S. DOE Office of Science User Facility.

Funders	Funder number
BlueRidge cluster
Center for Nanophase Materials Sciences
HERE
University of Utah MRSEC	DMR 11-21252
National Science Foundation	CBET-1461842
Office of Science
Oak Ridge National Laboratory
Automotive Research Center

Access to Document

10.1021/acs.jpclett.5b02378

Cite this

@article{288a15b1e4f8479596c5ce98720ec7bc,

title = "Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging",

abstract = "Molecular simulations of the diffusion of EMIM+ and TFSI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching 5 × 10-9 m2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.",

author = "Yadong He and Rui Qiao and Jenel Vatamanu and Oleg Borodin and Dmitry Bedrov and Jingsong Huang and Sumpter, {Bobby G.}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2016",

month = jan,

day = "7",

doi = "10.1021/acs.jpclett.5b02378",

language = "English",

volume = "7",

pages = "36--42",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

AU - He, Yadong

AU - Qiao, Rui

AU - Vatamanu, Jenel

AU - Borodin, Oleg

AU - Bedrov, Dmitry

AU - Huang, Jingsong

AU - Sumpter, Bobby G.

PY - 2016/1/7

Y1 - 2016/1/7

N2 - Molecular simulations of the diffusion of EMIM+ and TFSI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching 5 × 10-9 m2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

AB - Molecular simulations of the diffusion of EMIM+ and TFSI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching 5 × 10-9 m2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

UR - http://www.scopus.com/inward/record.url?scp=84954171993&partnerID=8YFLogxK

U2 - 10.1021/acs.jpclett.5b02378

DO - 10.1021/acs.jpclett.5b02378

M3 - Article

AN - SCOPUS:84954171993

SN - 1948-7185

VL - 7

SP - 36

EP - 42

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

IS - 1

ER -

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

Abstract

Bibliographical note

Funding

Access to Document

Other files and links

Fingerprint

Cite this