Ion Mobilities, Transference Numbers, and Inverse Haven Ratios of Polymeric Ionic Liquids

Zhang, Zidan; Wheatle, Bill K.; Krajniak, Jakub; Keith, Jordan R.; Ganesan, Venkat

doi:10.1021/acsmacrolett.9b00908

Title: Ion Mobilities, Transference Numbers, and Inverse Haven Ratios of Polymeric Ionic Liquids

Journal Article · 30 December 2019 · ACS Macro Letters

DOI: https://doi.org/10.1021/acsmacrolett.9b00908 · OSTI ID:2405987

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University of Texas at Austin, TX (United States); University of Texas at Austin
University of Texas at Austin, TX (United States)
Independent researcher, Poznan (Poland)

We probe the ion mobilities, transference numbers, and inverse Haven ratio of ionic liquids and polymerized ionic liquids as a function of their molecular weight using a combination of atomistic equilibrium and nonequilibrium molecular dynamics simulations. In contrast to expectations, we demonstrate that the inverse Haven ratio increases with increasing degree of polymerization (N) and then decreases at larger N. For a fixed center of mass reference frame, we demonstrate that such results arise as a consequence of the strong cation–cation correlated motions, which exceed (in magnitude) the selfdiffusivity of cations. Together, our findings challenge the premise underlying the pursuit of pure polymeric ionic liquids as high transference number, single-ion conducting electrolytes.

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Research Organization:: University of Texas at Austin, TX (United States)

Sponsoring Organization:: Robert A. Welch Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019272

OSTI ID:: 2405987

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 1 Vol. 9; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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