Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids

Zhang, Zidan; Sass, Jacob; Krajniak, Jakub; Ganesan, Venkat

doi:10.1021/acsmacrolett.2c00401

Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids

Journal Article · Tue Oct 25 00:00:00 EDT 2022 · ACS Macro Letters

DOI:https://doi.org/10.1021/acsmacrolett.2c00401· OSTI ID:2405985

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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)

Recently, significant interest has arisen on the impact of dynamical ion correlations on the conductivity and transport properties of polymeric electrolyte materials. It has been hypothesized that confining ion motion to narrow channels may reduce such ion correlations and enhance the resulting ionic conductivity. Motivated by such considerations, in this study we used a multiscale simulation framework to study the dynamical ion correlations in the microphase-separated lamella phase of block copolymeric ionic liquids and compare with the corresponding results for homopolymeric systems. We probed the influence of ion correlations through the partial ionicity, Δ, which quantifies the ratio of true conductivity to the ideal, Nernst–Einstein conductivity for the anion-related contributions. Consistent with our original hypothesis, our results demonstrate that the partial ionicity relating to the mobile anions is much larger in the lamella phases of block copolymers compared to that in homopolymers. Analysis of the distinct conductivity contributions demonstrates that such results arise as a result of an intricate compensation among the nonideal dynamical correlations relating to anions in lamella phases. Overall, our results suggest that self-assembled phases of block copolymers may provide an avenue to tune the dynamical ion correlations in polymer electrolyte systems.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0019272

OSTI ID:: 2405985

Alternate ID(s):: OSTI ID: 2406264

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 11 Vol. 11; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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