{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T12:46:55Z","timestamp":1792673215538,"version":"4.5.0"},"reference-count":44,"publisher":"American Chemical Society (ACS)","issue":"42","license":[{"start":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T00:00:00Z","timestamp":1791331200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T00:00:00Z","timestamp":1791331200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T00:00:00Z","timestamp":1791331200000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100007063","name":"University of Delhi","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100007063","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,22]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The development of solid polymer electrolytes for lithium batteries requires a molecular-level understanding of how host architecture and additives jointly control ion transport. Here, classical molecular dynamics simulations, complemented by density-functional theory, are used to investigate the independent effects of polyacrylonitrile (PAN) chain length and fluoroethylene carbonate (FEC) plasticizer content on lithium-ion transport and solvation in the PAN\u2013LiFSI\u2013FEC system. Increasing the chain length is found to suppress lithium diffusion, as longer chains progressively cage the cation within the nitrile coordination environment. Incorporation of FEC enhances the ionic conductivity by more than an order of magnitude, saturating over a broad 30\u201340 wt % range, despite a concurrent increase in bulk density that rules out a simple free-volume mechanism. Radial-distribution and residence-time analyses reveal that FEC does not enter the lithium first coordination shell but instead acts as a second-sphere plasticizer that renders the lithium\u2013polymer coordination dynamically labile; the diffusion coefficient correlates strongly and inversely with the coordination residence time. Density-functional calculations show that FEC binds lithium more strongly than the polymer nitrile, demonstrating that its exclusion from the first shell is entropic and steric rather than energetic. These results establish a coordination-dynamics mechanism for plasticizer-enhanced transport and identify a plasticized intermediate-length PAN host as a favorable electrolyte design.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c04366","type":"journal-article","created":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T21:01:36Z","timestamp":1791406896000},"page":"11333-11345","source":"Crossref","is-referenced-by-count":0,"title":["Effect of Polymer\nChain Length and Fluoroethylene\nCarbonate Plasticizer on Lithium-Ion Transport in PAN\u2013LiFSI\nSolid Polymer Electrolytes: A Molecular Dynamics Study"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2019-2033","authenticated-orcid":true,"given":"Alok Kumar","family":"Tripathi","sequence":"first","affiliation":[{"name":"Ramjas College, University of Delhi , , ,","place":["Delhi, India, 110007"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,7]]},"reference":[{"issue":"4","key":"2026102207414967900_cit1","doi-asserted-by":"publisher","first-page":"16103","DOI":"10.1038\/natrevmats.2016.103","article-title":"Lithium Battery Chemistries Enabled by Solid-State\nElectrolytes","volume":"2","author":"Manthiram","year":"2017","journal-title":"Nat. Rev. Mater."},{"issue":"9","key":"2026102207414967900_cit2","doi-asserted-by":"publisher","first-page":"2326","DOI":"10.1016\/j.chempr.2019.05.009","article-title":"Polymer Electrolytes\nfor Lithium-Based Batteries: Advances and Prospects","volume":"5","author":"Zhou","year":"2019","journal-title":"Chem"},{"issue":"2","key":"2026102207414967900_cit3","doi-asserted-by":"publisher","first-page":"183","DOI":"10.1016\/S0378-7753(98)00193-1","article-title":"Review of Gel-Type Polymer Electrolytes\nfor Lithium-Ion Batteries","volume":"77","author":"Song","year":"1999","journal-title":"J. Power Sources"},{"key":"2026102207414967900_cit4","doi-asserted-by":"publisher","first-page":"100643","DOI":"10.1016\/j.mtener.2021.100643","article-title":"Ionic Liquid\u2013Based\nSolid Electrolytes (Ionogels) for Application in Rechargeable Lithium\nBattery","volume":"20","author":"Tripathi","year":"2021","journal-title":"Mater. Today Energy"},{"issue":"10","key":"2026102207414967900_cit5","doi-asserted-by":"publisher","first-page":"4743","DOI":"10.1016\/S0032-3861(00)00831-4","article-title":"Lithium Complex\nin Polyacrylonitrile\/EC\/PC Gel-Type Electrolyte","volume":"42","author":"Chu","year":"2001","journal-title":"Polymer"},{"key":"2026102207414967900_cit6","doi-asserted-by":"publisher","first-page":"582","DOI":"10.1016\/j.jcis.2024.03.166","article-title":"Composition Regulation of Polyacrylonitrile-Based\nPolymer Electrolytes Enabling Dual-Interfacially Stable Solid-State\nLithium Batteries","volume":"665","author":"Liu","year":"2024","journal-title":"J. Colloid Interface Sci."},{"issue":"8\u20139","key":"2026102207414967900_cit7","doi-asserted-by":"publisher","first-page":"1249","DOI":"10.1016\/S0013-4686(99)00328-X","article-title":"Novel High\nSalt Content Polymer Electrolytes\nBased on High Tg Polymers","volume":"45","author":"Forsyth","year":"2000","journal-title":"Electrochim. Acta"},{"issue":"9","key":"2026102207414967900_cit8","doi-asserted-by":"publisher","first-page":"A148","DOI":"10.1149\/1.1390455","article-title":"Ion Transport in Polyacrylonitrile-Based\nElectrolytes with High LiTFSI Contents","volume":"4","author":"Wang","year":"2001","journal-title":"Electrochem.\nSolid-State Lett."},{"issue":"10","key":"2026102207414967900_cit9","doi-asserted-by":"publisher","first-page":"1594","DOI":"10.1021\/acsmacrolett.5c00576","article-title":"Branched Polyacrylonitrile\nEnabling Highly Lithium-Ion-Conductive Polymer Plastic Crystal Electrolytes","volume":"14","author":"Liu","year":"2025","journal-title":"ACS Macro Lett."},{"issue":"11","key":"2026102207414967900_cit10","doi-asserted-by":"publisher","first-page":"4141","DOI":"10.1021\/acs.macromol.9b02742","article-title":"Perspectives for Polymer Electrolytes:\nA View from\nFundamentals of Ionic Conductivity","volume":"53","author":"Bocharova","year":"2020","journal-title":"Macromolecules"},{"issue":"4","key":"2026102207414967900_cit11","doi-asserted-by":"publisher","first-page":"1620","DOI":"10.1021\/ma052277v","article-title":"Mechanism of Ion\nTransport in Amorphous Poly(Ethylene\nOxide)\/LiTFSI from Molecular Dynamics Simulations","volume":"39","author":"Borodin","year":"2006","journal-title":"Macromolecules"},{"issue":"4","key":"2026102207414967900_cit12","doi-asserted-by":"publisher","first-page":"2028","DOI":"10.1021\/ma901893h","article-title":"Understanding the Lithium Transport\nwithin a Rouse-Based Model for a PEO\/LiTFSI Polymer Electrolyte","volume":"43","author":"Diddens","year":"2010","journal-title":"Macromolecules"},{"issue":"8","key":"2026102207414967900_cit13","doi-asserted-by":"publisher","first-page":"1123","DOI":"10.1021\/acs.accounts.3c00791","article-title":"Ion Transport\nin Polymer Electrolytes: Building New Bridges between Experiment and\nMolecular Simulation","volume":"57","author":"Shao","year":"2024","journal-title":"Acc. 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Mater."},{"issue":"7","key":"2026102207414967900_cit16","doi-asserted-by":"publisher","first-page":"8169","DOI":"10.1021\/acsami.0c18414","article-title":"Effect of Fluoroethylene Carbonate Additives on the\nInitial Formation of the Solid Electrolyte Interphase on an Oxygen-Functionalized\nGraphitic Anode in Lithium-Ion Batteries","volume":"13","author":"Intan","year":"2021","journal-title":"ACS\nAppl. Mater. Interfaces"},{"issue":"22","key":"2026102207414967900_cit17","doi-asserted-by":"publisher","first-page":"8149","DOI":"10.1021\/acs.chemmater.6b02282","article-title":"Fluoroethylene Carbonate and Vinylene\nCarbonate Reduction: Understanding Lithium-Ion Battery Electrolyte\nAdditives and Solid Electrolyte Interphase Formation","volume":"28","author":"Michan","year":"2016","journal-title":"Chem. 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Chem. Theory Comput."},{"issue":"12","key":"2026102207414967900_cit30","doi-asserted-by":"publisher","first-page":"6131","DOI":"10.1021\/acs.jctc.7b00520","article-title":"Revisiting\nOPLS Force Field Parameters for Ionic Liquid Simulations","volume":"13","author":"Doherty","year":"2017","journal-title":"J. Chem. Theory Comput."},{"issue":"25","key":"2026102207414967900_cit31","doi-asserted-by":"publisher","first-page":"5071","DOI":"10.1021\/j150643a008","article-title":"Hydration and Mobility\nof Ions in\nSolution","volume":"87","author":"Impey","year":"1983","journal-title":"J. Phys. Chem."},{"issue":"18","key":"2026102207414967900_cit32","doi-asserted-by":"publisher","first-page":"2110","DOI":"10.1002\/qua.24481","article-title":"Jaguar: A High-performance Quantum\nChemistry Software Program with Strengths in Life and Materials Sciences","volume":"113","author":"Bochevarov","year":"2013","journal-title":"Int. J. of Quantum Chemistry"},{"issue":"15","key":"2026102207414967900_cit33","doi-asserted-by":"publisher","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A Consistent and Accurate Ab Initio Parametrization of Density Functional Dispersion\nCorrection (DFT-D) for the 94 Elements H-Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"issue":"6","key":"2026102207414967900_cit34","doi-asserted-by":"publisher","first-page":"581","DOI":"10.1063\/1.1699711","article-title":"Second-Order Transition\nTemperatures and Related Properties\nof Polystyrene. I. Influence of Molecular Weight","volume":"21","author":"Fox","year":"1950","journal-title":"Journal of Applied Physics"},{"issue":"28","key":"2026102207414967900_cit35","doi-asserted-by":"publisher","first-page":"36878","DOI":"10.1021\/acsami.4c04491","article-title":"Deep-Learning Interatomic Potential\nConnects Molecular Structural Ordering to the Macroscale Properties\nof Polyacrylonitrile","volume":"16","author":"Chahal","year":"2024","journal-title":"ACS Appl. Mater. Interfaces"},{"issue":"1","key":"2026102207414967900_cit36","doi-asserted-by":"publisher","first-page":"18","DOI":"10.1016\/j.ssi.2011.09.021","article-title":"Effect of Molecular\nWeight on Conductivity of Polymer Electrolytes","volume":"203","author":"Teran","year":"2011","journal-title":"Solid State Ionics"},{"key":"2026102207414967900_cit37","doi-asserted-by":"publisher","first-page":"125969","DOI":"10.1016\/j.polymer.2023.125969","article-title":"Ordered and Amorphous Phases of Polyacrylonitrile:\nEffect of Tensile Deformation of Structure on Relaxation and Glass\nTransition","volume":"277","author":"Yao","year":"2023","journal-title":"Polymer"},{"issue":"21","key":"2026102207414967900_cit38","doi-asserted-by":"publisher","first-page":"8014","DOI":"10.1039\/c2ra21290k","article-title":"Li+ Cation\nCoordination by Acetonitrile\u2013Insights from Crystallography","volume":"2","author":"Seo","year":"2012","journal-title":"RSC Adv."},{"issue":"4","key":"2026102207414967900_cit39","doi-asserted-by":"publisher","first-page":"040511","DOI":"10.1149\/1945-7111\/abf0d8","article-title":"Ion Pairing,\nClustering and Transport in a LiFSI-TMP\nElectrolyte as Functions of Salt Concentration Using Molecular Dynamics\nSimulations","volume":"168","author":"Galvez-Aranda","year":"2021","journal-title":"J. Electrochem. Soc."},{"issue":"21","key":"2026102207414967900_cit40","doi-asserted-by":"publisher","first-page":"214903","DOI":"10.1063\/5.0087824","article-title":"Effect of\nSuccinonitrile on Ion Transport in PEO-Based Lithium-Ion Battery Electrolytes","volume":"156","author":"Mohapatra","year":"2022","journal-title":"J. Chem. Phys."},{"issue":"1","key":"2026102207414967900_cit41","doi-asserted-by":"publisher","first-page":"4","DOI":"10.3390\/atoms4010004","article-title":"Density Functional\nTheory (DFT) Study on the Ternary\nInteraction System of the Fluorinated Ethylene Carbonate, Li+ and\nGraphene Model","volume":"4","author":"Mutoh","year":"2016","journal-title":"Atoms"},{"issue":"13","key":"2026102207414967900_cit42","doi-asserted-by":"publisher","first-page":"136001","DOI":"10.1103\/PhysRevLett.122.136001","article-title":"Correlations from Ion Pairing and the Nernst-Einstein\nEquation","volume":"122","author":"France-Lanord","year":"2019","journal-title":"Phys. Rev. Lett."},{"key":"2026102207414967900_cit43","doi-asserted-by":"publisher","first-page":"116304","DOI":"10.1016\/j.ssi.2023.116304","article-title":"Effects of\nSolvents on Li+ Distribution and Dynamics\nin PVDF\/LiFSI Solid Polymer Electrolytes: An All-Atom Molecular Dynamics\nSimulation Study","volume":"399","author":"Lemaalem","year":"2023","journal-title":"Solid State Ionics"},{"issue":"21","key":"2026102207414967900_cit44","doi-asserted-by":"publisher","first-page":"7882","DOI":"10.1021\/acs.macromol.5b01724","article-title":"Effect of Molecular\nWeight and Salt\nConcentration on Ion Transport and the Transference Number in Polymer\nElectrolytes","volume":"48","author":"Timachova","year":"2015","journal-title":"Macromolecules"}],"container-title":["The Journal of Physical\nChemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.6c04366","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/42\/11333\/68779072\/acs.jpcb.6c04366.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/130\/42\/11333\/68779072\/acs.jpcb.6c04366.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T12:10:07Z","timestamp":1792671007000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/130\/42\/11333\/5446594\/Effect-of-Polymer-Chain-Length-and-Fluoroethylene"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,10,7]]},"references-count":44,"journal-issue":{"issue":"42","published-online":{"date-parts":[[2026,10,7]]},"published-print":{"date-parts":[[2026,10,22]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.6c04366","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,10,7]]}}}