Low-Voltage Ligand-to-Metal Charge Transfer in LixCoO2

Low-Voltage Ligand-to-Metal Charge Transfer in LixCoO2 | 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 Low-Voltage Ligand-to-Metal Charge Transfer in Li x CoO 2 Faisal Alamgir, Abiram Krishnan, Sang-Jun Lee, Hirohito Ogasawara This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7272914/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Oxygen redox in transition metal oxide cathodes is typically expected to occur at higher voltages. Here, we report an unexpected low-voltage oxygen redox mechanism in the archetypal LiCoO 2 (LCO) cathode. This mechanism is triggered by changes to the local atomic structure from a subtle phase change within the first 10% of delithiation. Our results indicate the formation of delocalized electron holes at oxygen 2p orbitals resulting in a reduction of cobalt ions via ligand-to-metal charge transfer. This reduction causes an anomalous change in LCO’s magnetic response with delithiation. This observation provides fundamental insight into the mechanism behind anion redox, offering a fresh perspective to take advantage of this additional redox center. Physical sciences/Materials science/Materials for energy and catalysis/Batteries Physical sciences/Chemistry/Electrochemistry/Batteries Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SupplementaryInformation.docx Supplementary Information Cite Share Download PDF Status: Under Review 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. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. 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-7272914","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":509250856,"identity":"20f028d8-1ef3-43f9-83ec-a4a6262cd729","order_by":0,"name":"Faisal Alamgir","email":"data:image/png;base64,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","orcid":"","institution":"Georgia Institute of Technology","correspondingAuthor":true,"prefix":"","firstName":"Faisal","middleName":"","lastName":"Alamgir","suffix":""},{"id":509250857,"identity":"65f8d636-aaee-48f4-8570-bb07fcc5d525","order_by":1,"name":"Abiram Krishnan","email":"","orcid":"https://orcid.org/0000-0003-3311-1172","institution":"Georgia Institute of Technology","correspondingAuthor":false,"prefix":"","firstName":"Abiram","middleName":"","lastName":"Krishnan","suffix":""},{"id":509250858,"identity":"2567aa1a-8f78-402d-aef8-a1288e5bf93c","order_by":2,"name":"Sang-Jun Lee","email":"","orcid":"https://orcid.org/0000-0002-8199-3993","institution":"SLAC National Accelerator Laboratory","correspondingAuthor":false,"prefix":"","firstName":"Sang-Jun","middleName":"","lastName":"Lee","suffix":""},{"id":509250859,"identity":"417aa89c-66c3-4aa4-8aa9-0a24c312f754","order_by":3,"name":"Hirohito Ogasawara","email":"","orcid":"https://orcid.org/0000-0001-5338-1079","institution":"SLAC National Accelerator Laboratory","correspondingAuthor":false,"prefix":"","firstName":"Hirohito","middleName":"","lastName":"Ogasawara","suffix":""}],"badges":[],"createdAt":"2025-08-01 16:05:56","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-7272914/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-7272914/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":91819590,"identity":"2f52722a-d3e7-40e3-8833-8bfddbd9c3cb","added_by":"auto","created_at":"2025-09-22 07:07:11","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1057395,"visible":true,"origin":"","legend":"","description":"","filename":"ManuscriptFile.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7272914/v1_covered_a11282b0-96cb-49d0-91e2-0aa056718146.pdf"},{"id":91819184,"identity":"e4ff2a7a-6b26-4241-8c6e-b9f5dbee1801","added_by":"auto","created_at":"2025-09-22 07:06:13","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2176460,"visible":true,"origin":"","legend":"Supplementary Information","description":"","filename":"SupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-7272914/v1/958026364528122513ad4779.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"\u003cp\u003eLow-Voltage Ligand-to-Metal Charge Transfer in Li\u003csub\u003ex\u003c/sub\u003eCoO\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"nature-portfolio","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"","title":"Nature Portfolio","twitterHandle":"","acdcEnabled":false,"dfaEnabled":false,"editorialSystem":"ejp","reportingPortfolio":"","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-7272914/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7272914/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eOxygen redox in transition metal oxide cathodes is typically expected to occur at higher voltages. 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