Molecular dynamics based study on the effects of cation size on the local structure and diffusion in polymerized ionic liquids

Gillespie, Colin [ORNL] (ORCID:0000000320287080); Zhu, Qinyu [ORNL] (ORCID:0000000226402214); Riggleman, Robert [ORNL]; Kumar, Rajeev [ORNL] (ORCID:0000000194943488)

doi:10.1063/5.0341029

DOE OSTI · 3740497

Molecular dynamics based study on the effects of cation size on the local structure and diffusion in polymerized ionic liquids

Gillespie, Colin [ORNL] (ORCID:0000000320287080)·Zhu, Qinyu [ORNL] (ORCID:0000000226402214)·Riggleman, Robert [ORNL]·Kumar, Rajeev [ORNL] (ORCID:0000000194943488)

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Abstract

We have used coarse-grained molecular dynamics simulations to understand the effect of cation size on ion diffusion in polymerized ionic liquids at temperatures well above the glass transition temperature of the polymers. We investigated dependencies of the diffusion constant on the cation radius and static dielectric constant and interpreted these results in terms of underlying structural changes, and decoupling phenomenon. We have found non-monotonic effects of the cation radius on the diffusion constant, with a maximum at an intermediate radius resulting from two different size dependent effects. Changes in the radial distribution functions characterizing spatial distribution of cations with respect to anions result in a monotonic increase in the coordination number. This yields an increase in the effective interaction energy as a function of cation radius, which can explain the decrease in the diffusion constant. This increase is counteracted at small cation radii by a corresponding increase in decoupling of cation and anion dynamics. In addition, the diffusion constant is found to increase on increasing the static dielectric constant for all radii of the cations. These results highlight the significant role of decoupling in designing polymerized ionic liquids with an enhanced diffusion constant of cations.

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Gillespie, Colin [ORNL] (ORCID:0000000320287080), Zhu, Qinyu [ORNL] (ORCID:0000000226402214), Riggleman, Robert [ORNL], Kumar, Rajeev [ORNL] (ORCID:0000000194943488). 2026-09-01. Molecular dynamics based study on the effects of cation size on the local structure and diffusion in polymerized ionic liquids. https://doi.org/10.1063/5.0341029

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