Extraction of CaFexMn1-xO3-δ Perovskite Reduction/Re-oxidation Thermodynamics via the CrossFit CEF Algorithm: A Thermochemical Energy Storage Application

Extraction of CaFexMn1-xO3-δ Perovskite Reduction/Re-oxidation Thermodynamics via the CrossFit CEF Algorithm: A Thermochemical Energy Storage Application | 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 Extraction of CaFe x Mn 1-x O 3-δ Perovskite Reduction/Re-oxidation Thermodynamics via the CrossFit CEF Algorithm: A Thermochemical Energy Storage Application Steven A. Wilson, Zoe Liberman-Martin, Matthew A. Park, Alicia Bayon, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8388360/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 17 Mar, 2026 Read the published version in Discover Chemical Engineering → Version 1 posted 11 You are reading this latest preprint version Abstract Thermochemical energy storage (TCES) offers a pathway to store surplus electricity or heat as combined chemical plus thermal energy with high density, long-duration capability, and the ability to transport stored energy as stable solids. This study investigates an understudied material family for TCES by determining the temperature- and composition-dependent redox thermodynamics of CaFe x Mn 1−x O 3−δ (CFM, 0 ≤ x ≤ 1) using the CrossFit Compound Energy Formalism (CF-CEF) algorithm. CF-CEF combines ab initio density functional theory (DFT) calculations with thermogravimetric (TGA) data to extract reduction and re-oxidation thermodynamics. We compare TCES capacities of CFM with those of CaAl 0.2 Mn 0.8 O 3−δ (CAM28), a benchmark material. The Fe-lean composition (x = 0.0625) achieves a thermochemical storage capacity of 53 kJ·mol⁻¹ O at a re-oxidation temperature of 760°C and a reduction temperature of 1250°C (ΔT = 490°C), excluding sensible heat, exceeding CAM28 by about 20%, and reaching a max of 60 kJ/mol at ΔT = 850°C. These findings identify Fe-lean CFM as a promising candidate for next-generation thermochemical energy storage. Full Text Additional Declarations No competing interests reported. Supplementary Files CFMSI.docx Cite Share Download PDF Status: Published Journal Publication published 17 Mar, 2026 Read the published version in Discover Chemical Engineering → Version 1 posted Editorial decision: Revision requested 05 Feb, 2026 Reviews received at journal 31 Jan, 2026 Reviewers agreed at journal 21 Jan, 2026 Reviewers agreed at journal 19 Jan, 2026 Reviews received at journal 14 Jan, 2026 Reviewers agreed at journal 13 Jan, 2026 Reviewers invited by journal 12 Jan, 2026 Editor invited by journal 12 Jan, 2026 Editor assigned by journal 23 Dec, 2025 Submission checks completed at journal 23 Dec, 2025 First submitted to journal 17 Dec, 2025 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-8388360","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":573959157,"identity":"05a21836-0cab-411e-9ac6-d32c9763afc0","order_by":0,"name":"Steven A. 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08:25:09","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1496842,"visible":true,"origin":"","legend":"","description":"","filename":"CFMSI.docx","url":"https://assets-eu.researchsquare.com/files/rs-8388360/v1/25f54d2e96c9e4192197935d.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003eExtraction of CaFe\u003csub\u003ex\u003c/sub\u003eMn\u003csub\u003e1-x\u003c/sub\u003eO\u003csub\u003e3-δ\u003c/sub\u003e Perovskite Reduction/Re-oxidation Thermodynamics via the CrossFit CEF Algorithm: A Thermochemical Energy Storage Application\u003c/p\u003e","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"discover-chemical-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dice","sideBox":"Learn more about [Discover Chemical Engineering](https://www.springer.com/journal/43938)","snPcode":"","submissionUrl":"","title":"Discover Chemical Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8388360/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8388360/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThermochemical energy storage (TCES) offers a pathway to store surplus electricity or heat as combined chemical plus thermal energy with high density, long-duration capability, and the ability to transport stored energy as stable solids. This study investigates an understudied material family for TCES by determining the temperature- and composition-dependent redox thermodynamics of CaFe\u003csub\u003ex\u003c/sub\u003eMn\u003csub\u003e1\u0026minus;x\u003c/sub\u003eO\u003csub\u003e3\u0026minus;δ\u003c/sub\u003e (CFM, 0\u0026thinsp;\u0026le;\u0026thinsp;x\u0026thinsp;\u0026le;\u0026thinsp;1) using the CrossFit Compound Energy Formalism (CF-CEF) algorithm. CF-CEF combines \u003cem\u003eab initio\u003c/em\u003e density functional theory (DFT) calculations with thermogravimetric (TGA) data to extract reduction and re-oxidation thermodynamics. We compare TCES capacities of CFM with those of CaAl\u003csub\u003e0.2\u003c/sub\u003eMn\u003csub\u003e0.8\u003c/sub\u003eO\u003csub\u003e3\u0026minus;δ\u003c/sub\u003e (CAM28), a benchmark material. The Fe-lean composition (x\u0026thinsp;=\u0026thinsp;0.0625) achieves a thermochemical storage capacity of 53 kJ\u0026middot;mol⁻\u0026sup1; O at a re-oxidation temperature of 760\u0026deg;C and a reduction temperature of 1250\u0026deg;C (ΔT\u0026thinsp;=\u0026thinsp;490\u0026deg;C), excluding sensible heat, exceeding CAM28 by about 20%, and reaching a max of 60 kJ/mol at ΔT\u0026thinsp;=\u0026thinsp;850\u0026deg;C. These findings identify Fe-lean CFM as a promising candidate for next-generation thermochemical energy storage.\u003c/p\u003e","manuscriptTitle":"Extraction of CaFexMn1-xO3-δ Perovskite Reduction/Re-oxidation Thermodynamics via the CrossFit CEF Algorithm: A Thermochemical Energy Storage Application","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-14 08:24:08","doi":"10.21203/rs.3.rs-8388360/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-02-05T05:45:54+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-31T23:22:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"302908665578029664629297619728007745445","date":"2026-01-22T03:53:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"164029722533689614059220789238741450727","date":"2026-01-19T17:37:12+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-14T14:08:32+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"109677141464624107820915339904635151113","date":"2026-01-13T13:31:46+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-01-12T20:59:48+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2026-01-12T09:11:31+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-23T07:53:33+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-12-23T07:50:58+00:00","index":"","fulltext":""},{"type":"submitted","content":"Discover Chemical Engineering","date":"2025-12-17T17:48:48+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"discover-chemical-engineering","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"dice","sideBox":"Learn more about [Discover Chemical Engineering](https://www.springer.com/journal/43938)","snPcode":"","submissionUrl":"","title":"Discover Chemical Engineering","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Discover Series","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"cb6b5f27-59b2-4388-aa52-61601725b40a","owner":[],"postedDate":"January 14th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2026-03-23T16:06:18+00:00","versionOfRecord":{"articleIdentity":"rs-8388360","link":"https://doi.org/10.1007/s43938-026-00115-1","journal":{"identity":"discover-chemical-engineering","isVorOnly":false,"title":"Discover Chemical Engineering"},"publishedOn":"2026-03-17 15:58:12","publishedOnDateReadable":"March 17th, 2026"},"versionCreatedAt":"2026-01-14 08:24:08","video":"","vorDoi":"10.1007/s43938-026-00115-1","vorDoiUrl":"https://doi.org/10.1007/s43938-026-00115-1","workflowStages":[]},"version":"v1","identity":"rs-8388360","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8388360","identity":"rs-8388360","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}