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| Autores principales: | , , , , |
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| Formato: | Preprint |
| Publicado: |
2026
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| Materias: | |
| Acceso en línea: | https://arxiv.org/abs/2606.01978 |
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| _version_ | 1866913179101036544 |
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| author | Jani, Aicha Gravelle, Simon Wzietek, Pawel Zeghal, Mehdi Judeinstein, Patrick |
| author_facet | Jani, Aicha Gravelle, Simon Wzietek, Pawel Zeghal, Mehdi Judeinstein, Patrick |
| contents | Ion transport in glyme-based electrolytes arises from a complex interplay between solvation structure, ion correlations, and polymer chain length. Here, combining pulsed-field gradient nuclear magnetic resonance (PFG-NMR), ionic conductivity measurements, and molecular dynamics (MD) simulations, we investigate the diffusion of monovalent cations (Li$^+$, Na$^+$, Cs$^+$) and TFSI$^-$ anions across a wide molecular-weight range, from monoglyme to long poly(ethylene oxide) (PEO) chains up to 4000~g/mol, corresponding to $n$ up to 88, where $n$ is the number of ethylene oxide repeat units. We identify a crossover region at $n \approx 8$ separating two transport regimes. For short chains, ion motion is consistent with a vehicular mechanism, accompanied by pronounced ion correlations. For longer chains, ion transport decouples from polymer motion and proceeds via rapid coordination exchanges within a slowly relaxing matrix. This transition is accompanied by reduced ion clustering and enhanced anion mobility, leading to increasingly anion-dominated charge transport. Overall, our results provide a molecular picture of ion transport across the molecular-to-polymeric transition and highlight the central role of solvation shell dynamics and polymer relaxation in governing ion dynamics in glyme-based electrolytes. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2606_01978 |
| institution | arXiv |
| publishDate | 2026 |
| record_format | arxiv |
| spellingShingle | Molecular-to-polymeric crossover in ion diffusion in glyme-based electrolytes: from vehicular to hopping transport Jani, Aicha Gravelle, Simon Wzietek, Pawel Zeghal, Mehdi Judeinstein, Patrick Soft Condensed Matter Ion transport in glyme-based electrolytes arises from a complex interplay between solvation structure, ion correlations, and polymer chain length. Here, combining pulsed-field gradient nuclear magnetic resonance (PFG-NMR), ionic conductivity measurements, and molecular dynamics (MD) simulations, we investigate the diffusion of monovalent cations (Li$^+$, Na$^+$, Cs$^+$) and TFSI$^-$ anions across a wide molecular-weight range, from monoglyme to long poly(ethylene oxide) (PEO) chains up to 4000~g/mol, corresponding to $n$ up to 88, where $n$ is the number of ethylene oxide repeat units. We identify a crossover region at $n \approx 8$ separating two transport regimes. For short chains, ion motion is consistent with a vehicular mechanism, accompanied by pronounced ion correlations. For longer chains, ion transport decouples from polymer motion and proceeds via rapid coordination exchanges within a slowly relaxing matrix. This transition is accompanied by reduced ion clustering and enhanced anion mobility, leading to increasingly anion-dominated charge transport. Overall, our results provide a molecular picture of ion transport across the molecular-to-polymeric transition and highlight the central role of solvation shell dynamics and polymer relaxation in governing ion dynamics in glyme-based electrolytes. |
| title | Molecular-to-polymeric crossover in ion diffusion in glyme-based electrolytes: from vehicular to hopping transport |
| topic | Soft Condensed Matter |
| url | https://arxiv.org/abs/2606.01978 |