Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles

Siqi Liu; Clemens Liedel; Nadezda V. Tarakina; Naresh C. Osti; Pinar Akcora

doi:10.1039/c9nr04204k

Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles

Siqi Liu, Clemens Liedel, Nadezda V. Tarakina, Naresh C. Osti, Pinar Akcora

Chemical Spectroscopy

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

13 Scopus citations

Abstract

We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM⁺ cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH₃) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM⁺ cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM⁺ is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH₃ is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.

Original language	English
Pages (from-to)	19832-19841
Number of pages	10
Journal	Nanoscale
Volume	11
Issue number	42
DOIs	https://doi.org/10.1039/c9nr04204k
State	Published - Nov 14 2019

Funding

This work was supported by the National Science Foundation DMR Polymer program under award #1807802. Neutron scattering experiments were conducted at the Oak Ridge National Laboratory’s Spallation Neutron Source with support from the Scientific User Facilities Division, Office of Basic Energy Science, U.S. Department of Energy (DOE). We thank Jessica Brandt and Steffen Tröger-Müller for help with the synthesis of the zwitterionic liquid.

Funders	Funder number
National Science Foundation DMR Polymer
Office of Basic Energy Science
Scientific User Facilities Division
National Science Foundation	1807802
U.S. Department of Energy
Oak Ridge National Laboratory

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abstract = "We incorporated polymer-grafted nanoparticles into ionic and zwitterionic liquids to explore the solvation and confinement effects on their heterogeneous dynamics using quasi-elastic neutron scattering (QENS). 1-Hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM-TFSI) mixed with deuterated poly(methyl methacrylate) (d-PMMA)-grafted nanoparticles is studied to unravel how dynamic coupling between PMMA and HMIM-TFSI influence the fast and slow diffusion characteristics of the HMIM+ cations. The zwitterionic liquid, 1-butyl-3-methyl imidazole-2-ylidene borane (BMIM-BH3) is critically selected and mixed with PMMA-grafted nanoparticles for comparison in this work as its ions do not self-dissociate and it does not couple with PMMA through ion-dipole interactions as HMIM-TFSI does. We find that long-range unrestricted diffusion of HMIM+ cations is higher in well-dispersed particles than in aggregated particle systems, whereas the localized diffusion of HMIM+ is measured to be higher in close-packed particles. Translational diffusion dynamics of BMIM-BH3 is not influenced by any particle structures suggesting that zwitterions do not interact with PMMA. This difference between two ionic liquid types enables us to decouple polymer effects from the diffusion of ionic liquids, which is integral to understand the ionic transport mechanism in ionic liquids confined in polymer-grafted nanoparticle electrolytes.",

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AU - Akcora, Pinar

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Dynamics of ionic liquids in the presence of polymer-grafted nanoparticles

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