Lowering the Barrier: Importance of A-Site Cation Chemistry in Superionic Halide Solid Electrolytes

Lowering the Barrier: Importance of A-Site Cation Chemistry in Superionic Halide Solid Electrolytes | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Lowering the Barrier: Importance of A-Site Cation Chemistry in Superionic Halide Solid Electrolytes Ieuan Seymour, Kit Barker, Sarah McKinney, Raul Artal, Ricardo Jimenez, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3981393/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 29 Aug, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Abstract Halide solid electrolytes do not currently display ionic conductivities suitable for high-power all-solid-state batteries. We explore the model system A 2 ZrCl 6 (A = Li, Na, Cu, Ag) to understand the fundamental role that A-site chemistry plays on fast ion transport. Having synthesised Ag 2 ZrCl 6 for the first time we reveal exceptional room temperature ionic conductivities in Cu 2 ZrCl 6 and Ag 2 ZrCl 6 of 1 × 10 −2 and 4 × 10 −3 S cm −1 , respectively. We introduce the concept that there are inherent limits to ionic conductivity in solids, where the energy and number of transition states play pivotal roles. Transport that involves multiple coordination changes along the pathway suffer from an intrinsic minimum activation energy. At certain lattice sizes, the energies of different coordinations can become equivalent, leading to remarkably lower barriers when a pathway involves a single coordination change. Our models provide a deeper understanding into the optimisation and design criteria for halide superionic conductors. Physical sciences/Materials science/Materials for energy and catalysis/Batteries Physical sciences/Materials science/Theory and computation/Atomistic models Physical sciences/Chemistry/Inorganic chemistry/Solid-state chemistry Full Text Additional Declarations There is NO Competing Interest. Supplementary Files LoweringthebarrierSI.docx Supplementary information file Cite Share Download PDF Status: Published Journal Publication published 29 Aug, 2024 Read the published version in Nature Communications → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3981393","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":278784963,"identity":"ea063319-4e0b-4133-a5a9-cad9437f2bf2","order_by":0,"name":"Ieuan Seymour","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0002-9550-9971","institution":"Imperial College London","correspondingAuthor":true,"prefix":"","firstName":"Ieuan","middleName":"","lastName":"Seymour","suffix":""},{"id":278784964,"identity":"d02c7abf-00c9-4c39-b08a-f51975d5435f","order_by":1,"name":"Kit Barker","email":"","orcid":"","institution":"Department of Materials, Imperial College London","correspondingAuthor":false,"prefix":"","firstName":"Kit","middleName":"","lastName":"Barker","suffix":""},{"id":278784965,"identity":"acc8bbfa-71dd-4687-b412-c4ec0ff47bc5","order_by":2,"name":"Sarah McKinney","email":"","orcid":"","institution":"Department of Chemistry, Imperial College London","correspondingAuthor":false,"prefix":"","firstName":"Sarah","middleName":"","lastName":"McKinney","suffix":""},{"id":278784966,"identity":"43d2719c-4704-4bf9-a484-f72945452d7b","order_by":3,"name":"Raul Artal","email":"","orcid":"","institution":"Instituto de Ciencia de Materiales de Madrid (ICMM - 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We explore the model system A\u003csub\u003e2\u003c/sub\u003eZrCl\u003csub\u003e6\u003c/sub\u003e (A = Li, Na, Cu, Ag) to understand the fundamental role that A-site chemistry plays on fast ion transport. Having synthesised Ag\u003csub\u003e2\u003c/sub\u003eZrCl\u003csub\u003e6\u003c/sub\u003e for the first time we reveal exceptional room temperature ionic conductivities in Cu\u003csub\u003e2\u003c/sub\u003eZrCl\u003csub\u003e6\u003c/sub\u003e and Ag\u003csub\u003e2\u003c/sub\u003eZrCl\u003csub\u003e6\u003c/sub\u003e of 1 × 10\u003csup\u003e−2\u003c/sup\u003e and 4 × 10\u003csup\u003e−3\u003c/sup\u003e S cm\u003csup\u003e−1\u003c/sup\u003e, respectively. We introduce the concept that there are inherent limits to ionic conductivity in solids, where the energy and number of transition states play pivotal roles. Transport that involves multiple coordination changes along the pathway suffer from an intrinsic minimum activation energy. At certain lattice sizes, the energies of different coordinations can become equivalent, leading to remarkably lower barriers when a pathway involves a single coordination change. 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