{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,25]],"date-time":"2026-10-25T06:10:38Z","timestamp":1792908638879,"version":"4.5.0"},"reference-count":74,"publisher":"AIP Publishing","issue":"20","funder":[{"DOI":"10.13039\/501100001843","name":"Science and Engineering Research Board","doi-asserted-by":"publisher","award":["CRG\/2022\/007119"],"award-info":[{"award-number":["CRG\/2022\/007119"]}],"id":[{"id":"10.13039\/501100001843","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Anusandhan National Research Foundation","award":["CRG\/2022\/007119"],"award-info":[{"award-number":["CRG\/2022\/007119"]}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2025,11,28]]},"abstract":"<jats:p>We investigate the impact of simultaneous addition of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMIMTFSI) ionic liquid and excess NaTFSI salt on the microscopic dynamics and transport properties of NaTFSI-based water-in-salt electrolyte (WiSE). From the analysis of the translational dynamics of the ions, we observe that the Na+ ions are the fastest diffusing ionic species stemming from their longer correlated motion with water molecules in the 8\u00a0m WiSE. As observed in experiments, the simulated ionic conductivity of the electrolyte decreases monotonically with increasing overall concentration of the electrolyte from 8 to 80\u00a0m by adding EMIMTFSI and NaTFSI together. The analysis of distinct diffusion coefficients reveals an overall anti-correlated collective motion of both coions and counterions in the WiSE (8\u00a0m) and hybrid electrolytes (50 and 80\u00a0m). Among these collective motions, the anion\u2013anion (TFSI\u2212\u2013TFSI\u2212) exhibits most pronounced anti-correlated motion. In the hybrid electrolytes, a longer residence time for the Na+ ions in the vicinity of water molecules is observed, signifying the dominance of the vehicular mechanism of Na+ ion conduction. On the other hand, Na+ and EMIM+ cations both adapt structural exchange mechanisms for their conduction when present in close proximity to the TFSI\u2212 anions in both WiSE and hybrid electrolytes. The presence of longer average hydrogen bond lifetimes between water molecules reveals stronger hydrogen bonds due to their small cluster-like existence in the hybrid electrolytes. The slower relaxation of the rotational time autocorrelation function for water and the EMIM+ cation with increasing salt concentration implies restriction in their motions due to the surrounding species. Pronounced dynamic heterogeneity in the motion of Na+ ions is observed in the hybrid electrolytes as compared to that in WiSE because of very different solvation environments in their vicinity. A longer correlation timescale for Na+ ions and water molecules is revealed through the analysis of distinct van Hove correlation functions in the hybrid electrolytes.<\/jats:p>","DOI":"10.1063\/5.0295948","type":"journal-article","created":{"date-parts":[[2025,11,26]],"date-time":"2025-11-26T11:32:39Z","timestamp":1764156759000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":2,"title":["Dynamic heterogeneity and mechanism of ionic transport in NaTFSI-based WiSE and superconcentrated NaTFSI\u2013EmimTFSI hybrid aqueous electrolytes"],"prefix":"10.1063","volume":"163","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2154-7684","authenticated-orcid":false,"given":"Navneet","family":"Singh","sequence":"first","affiliation":[{"name":"Department of Chemistry, Indian Institute of Technology Delhi 1 , Hauz Khas, New Delhi 110016,","place":["India"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9124-2918","authenticated-orcid":false,"given":"Hemant K.","family":"Kashyap","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Indian Institute of Technology Delhi 1 , Hauz Khas, New Delhi 110016,","place":["India"]},{"name":"Indian Institute of Technology Delhi-Abu Dhabi 2 , Khalifa City B, Abu Dhabi MZ29,","place":["United Arab Emirates"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,11,26]]},"reference":[{"key":"2025112606323093100_c1","doi-asserted-by":"publisher","first-page":"3529","DOI":"10.1039\/c6cs00776g","volume":"46","year":"2017","journal-title":"Chem. 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