Beyond Qualitative Diagnosis of Li Plating in Li-ion Batteries: A Critical-State Metric from Electrochemical Impedance Spectroscopy

Beyond Qualitative Diagnosis of Li Plating in Li-ion Batteries: A Critical-State Metric from Electrochemical Impedance Spectroscopy | 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 Research Article Beyond Qualitative Diagnosis of Li Plating in Li-ion Batteries: A Critical-State Metric from Electrochemical Impedance Spectroscopy Wenxuan Hu, Jianrong Lin, Yingao Zhou, Hongxin Lin, Wenhao Wu, and 9 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-9420766/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Lithium-ion batteries (LIBs)​ deployed in smart grid applications​ require extended cycle life and predictable safety performance​ through advanced battery management systems. Li plating, a major cause of capacity fade and thermal runaway, poses a critical challenge owing to its transient, heterogeneous nature and the lack of operando quantitative detection tools. To address this gap, we establish an operando quantitative framework​ for real-time monitoring​ of Li plating on graphite anodes. The proposed critical Li-plating areal capacity (q Li ), derived from dynamic electrochemical impedance spectroscopy (DEIS) enables precise calculation​ of Li deposition kinetics under various charging protocols. Multi-modal validation​ through operando solid-state nuclear magnetic resonance (ssNMR)-DEIS combined measurements, incremental capacity analysis (ICA), and mass spectrometry titration (MST)​ demonstrates​ the method’s robustness​ with high accuracy (R 2 > 0.97)​ across diverse charging conditions and battery configurations. Furthermore, accelerated aging under coupled conditions identifies critical thresholds: mild Li plating not only accelerates capacity fade, but also drives Li plating-boundary migration beyond the critical q Li , thereafter causing capacity plunge. This work advances both methodological frameworks—by establishing the first operando quantification platform for Li plating—and battery safety management strategies, offering safety alerting and adaptive charging protocols to keep plating below q Li and thereby extend cycle life. Lithium-ion batteries Li plating quantification dynamic electrochemical impedance spectroscopy operando solid-state NMR battery aging Full Text Additional Declarations No competing interests reported. Supplementary Files Supportinginformation1.docx Cite Share Download PDF Status: Posted 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-9420766","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":627407550,"identity":"346d2b7b-6a1d-4fbb-a050-a306e69e9b4e","order_by":0,"name":"Wenxuan Hu","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Wenxuan","middleName":"","lastName":"Hu","suffix":""},{"id":627407562,"identity":"9e52c6a1-851a-477e-acfe-4334a4bf3e99","order_by":1,"name":"Jianrong Lin","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Jianrong","middleName":"","lastName":"Lin","suffix":""},{"id":627407575,"identity":"27ed262b-0092-4144-b93b-c33406c0ad56","order_by":2,"name":"Yingao Zhou","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yingao","middleName":"","lastName":"Zhou","suffix":""},{"id":627407579,"identity":"c373dd81-b379-4ea2-8daa-d02d0b4a0275","order_by":3,"name":"Hongxin Lin","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Hongxin","middleName":"","lastName":"Lin","suffix":""},{"id":627407580,"identity":"0087bbda-481a-4efd-8e59-9b60b2a3a41a","order_by":4,"name":"Wenhao Wu","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Wenhao","middleName":"","lastName":"Wu","suffix":""},{"id":627407584,"identity":"50ed714d-74de-4209-a83a-a6293a4f33d0","order_by":5,"name":"Ying Lin","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Ying","middleName":"","lastName":"Lin","suffix":""},{"id":627407587,"identity":"f5f1850d-d38c-49b0-bc48-2bd329f3b384","order_by":6,"name":"Yonggang Hu","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yonggang","middleName":"","lastName":"Hu","suffix":""},{"id":627407592,"identity":"1ee69a5f-e582-45cd-93d6-a93f863edca6","order_by":7,"name":"Yufan Peng","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yufan","middleName":"","lastName":"Peng","suffix":""},{"id":627407596,"identity":"bac11d4f-5a1b-46e9-913d-096c518c6d5b","order_by":8,"name":"Xiaozhe Yu","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Xiaozhe","middleName":"","lastName":"Yu","suffix":""},{"id":627407598,"identity":"0dde26a9-d592-40ab-a354-0e4b352b6e26","order_by":9,"name":"Jinding Liang","email":"","orcid":"","institution":"Contemporary Amperex Technology Co., Ltd","correspondingAuthor":false,"prefix":"","firstName":"Jinding","middleName":"","lastName":"Liang","suffix":""},{"id":627407600,"identity":"8b1d7088-6df8-4ef1-ad1f-0728dfb543ff","order_by":10,"name":"Yimin Wei","email":"","orcid":"","institution":"Contemporary Amperex Technology Co., Ltd","correspondingAuthor":false,"prefix":"","firstName":"Yimin","middleName":"","lastName":"Wei","suffix":""},{"id":627407602,"identity":"7f0f5c0a-b482-499a-86d0-20f1142c8e27","order_by":11,"name":"Yanting Jin","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Yanting","middleName":"","lastName":"Jin","suffix":""},{"id":627407605,"identity":"01f94cc7-daa6-43a2-901d-80583649e9b4","order_by":12,"name":"Zhengliang Gong","email":"","orcid":"","institution":"Xiamen University","correspondingAuthor":false,"prefix":"","firstName":"Zhengliang","middleName":"","lastName":"Gong","suffix":""},{"id":627407608,"identity":"ad1b32b3-5a32-4edc-b339-f9466c603604","order_by":13,"name":"Yong Yang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAuElEQVRIiWNgGAWjYNCCCgglQYKWMyRrYWwjRYvBjeRnD7/OOxxtcID54G0eBrs8IrSkmRvLbkvL3XCALdmahyG5mAgtCWbSkttsgFp4zKR5GA4kNhDWkv5NWnKOBFAL/zditeSYSX5sANvCRpwWyTNvyqQZjqXlzjzMZmw5xyCZsBa+4+nbJH/UHM7tO9788MabCjvCWhQuJDAw84BYzGB3ElIPBPL9BxgYfxChcBSMglEwCkYwAADE+z4QrbiXBAAAAABJRU5ErkJggg==","orcid":"","institution":"Xiamen University","correspondingAuthor":true,"prefix":"","firstName":"Yong","middleName":"","lastName":"Yang","suffix":""}],"badges":[],"createdAt":"2026-04-15 02:38:39","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-9420766/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-9420766/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":109408738,"identity":"31d75e7d-1001-4355-b0f8-6efe5e35df74","added_by":"auto","created_at":"2026-05-17 14:25:15","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4670996,"visible":true,"origin":"","legend":"","description":"","filename":"Manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-9420766/v1_covered_d44f8aa5-13bb-4aa6-9406-a4a8a99daf94.pdf"},{"id":107690268,"identity":"2cb46dd8-f1c0-4b55-941c-033244cb8cab","added_by":"auto","created_at":"2026-04-24 05:43:59","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":23387466,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation1.docx","url":"https://assets-eu.researchsquare.com/files/rs-9420766/v1/bb3f2ff0fb4206d56a123d26.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Beyond Qualitative Diagnosis of Li Plating in Li-ion Batteries: A Critical-State Metric from Electrochemical Impedance Spectroscopy","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"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":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Lithium-ion batteries, Li plating quantification, dynamic electrochemical impedance spectroscopy, operando solid-state NMR, battery aging","lastPublishedDoi":"10.21203/rs.3.rs-9420766/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-9420766/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eLithium-ion batteries (LIBs)​ deployed in smart grid applications​ require extended cycle life and predictable safety performance​ through advanced battery management systems. Li plating, a major cause of capacity fade and thermal runaway, poses a critical challenge owing to its transient, heterogeneous nature and the lack of operando quantitative detection tools. To address this gap, we establish an operando quantitative framework​ for real-time monitoring​ of Li plating on graphite anodes. The proposed critical Li-plating areal capacity (q\u003csub\u003eLi\u003c/sub\u003e), derived from dynamic electrochemical impedance spectroscopy (DEIS) enables precise calculation​ of Li deposition kinetics under various charging protocols. Multi-modal validation​ through operando solid-state nuclear magnetic resonance (ssNMR)-DEIS combined measurements, incremental capacity analysis (ICA), and mass spectrometry titration (MST)​ demonstrates​ the method\u0026rsquo;s robustness​ with high accuracy (R\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;\u0026gt;\u0026thinsp;0.97)​ across diverse charging conditions and battery configurations. Furthermore, accelerated aging under coupled conditions identifies critical thresholds: mild Li plating not only accelerates capacity fade, but also drives Li plating-boundary migration beyond the critical q\u003csub\u003eLi\u003c/sub\u003e, thereafter causing capacity plunge. This work advances both methodological frameworks\u0026mdash;by establishing the first operando quantification platform for Li plating\u0026mdash;and battery safety management strategies, offering safety alerting and adaptive charging protocols to keep plating below q\u003csub\u003eLi\u003c/sub\u003e and thereby extend cycle life.\u003c/p\u003e","manuscriptTitle":"Beyond Qualitative Diagnosis of Li Plating in Li-ion Batteries: A Critical-State Metric from Electrochemical Impedance Spectroscopy","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-04-24 05:43:54","doi":"10.21203/rs.3.rs-9420766/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"79859868-bc52-4193-9aa4-b3892fd0d3f0","owner":[],"postedDate":"April 24th, 2026","published":true,"recentEditorialEvents":[{"type":"decision","content":"Revision requested","date":"2026-05-03T14:34:30+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-03T09:02:54+00:00","index":20,"fulltext":""},{"type":"reviewerAgreed","content":"152915037833195729470169135530659523911","date":"2026-04-30T14:55:50+00:00","index":19,"fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-05-17T14:25:02+00:00","versionOfRecord":[],"versionCreatedAt":"2026-04-24 05:43:54","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-9420766","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-9420766","identity":"rs-9420766","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}