{
  "abstract": "Understanding lithium-ion motion in concentrated ionic-liquid electrolytes requires a description that connects local coordination structure to long-range diffusion. Here we combine dispersioncorrected density functional theory (DFT), natural bond orbital (NBO) analysis, and classical molecular dynamics (MD) simulations to examine [EMI][TFSI]/LiFSI/EC/DMC electrolytes at 298 K. The calculations show that [TFSI]- and [FSI]- possess distinct interaction landscapes: six low-energy [EMI][TFSI] conformers span 0.676–5.170 kJ mol-1 in relative energy and −41.22 to −48.64 kJ mol-1 in interaction energy, whereas the corresponding [EMI][FSI] conformers span 0.163–5.849 kJ mol-1 and −34.62 to −44.19 kJ mol-1, respectively. In the condensed phase, Li+ coordination evolves from predominantly carbonate-mediated solvation in the 0% ionic-liquid system to mixed carbonate/anion coordination at 42.9% ionic-liquid content and exclusively anion coordination in the 100% ionic-liquid system. The Li+ self-diffusion coefficient is nonmonotonic across the reported compositions, decreasing from 28.66 × 10-12 m2 s-1 in the carbonate-rich system to 19.88 × 10-12 m2 s-1 at 42.9% ionic-liquid content and increasing to 27.00 × 10-12 m2 s-1 in the pure ionic-liquid system. FSI- also diffuses faster than TFSI- in the systems for which both are present. These results support a mechanistic picture in which Li+ motion is governed not solely by bulk solvent properties but by the persistence and reorganization of its local coordination environment. Building on this observation, we formulate a Coordination–Diffusion Coupling (CDC) framework that combines Shannon coordination entropy with trajectory-derived coordination exchange kinetics and a complementary timescale ratio between translational displacement and coordination-shell residence. The framework is presented as a physically motivated descriptor for interpreting and ultimately screening electrolyte compositions. Importantly, the present study does not directly calculate electrochemical stability, interfacial decomposition, or a local dielectric constant; those properties are therefore treated as design considerations rather than demonstrated outcomes.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Hawassa University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Abraham Molla Wagaye"
    },
    {
      "name": "Abraham molla Wagaye",
      "orcid": "0009-0002-4914-2029"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/ckvdzfn2v3k44.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008800/v1",
  "fulltext_url": null,
  "id": "ckvdzfn2v3k44",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008800/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "2208|Advanced Battery Materials and Technologies"
    ]
  ],
  "openalex": "W7213247493",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-14",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/ckvdzfn2v3k44.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008800",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008800/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Coordination–Diffusion Coupling (CDC) in Dual-Anion Ionic-Liquid/Carbonate Electrolytes: Molecular Origins of Lithium-Ion Self-Diffusion",
  "title_text": "Coordination–Diffusion Coupling (CDC) in Dual-Anion Ionic-Liquid/Carbonate Electrolytes: Molecular Origins of Lithium-Ion Self-Diffusion",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/ckvdzfn2v3k44",
  "venue": "ChemRxiv",
  "versions": []
}