{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T18:49:08Z","timestamp":1792003748092,"version":"4.4.0"},"reference-count":83,"publisher":"American Chemical Society (ACS)","issue":"40","license":[{"start":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T00:00:00Z","timestamp":1790553600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100017146","name":"Faraday Institution","doi-asserted-by":"publisher","award":["FIRG016"],"award-info":[{"award-number":["FIRG016"]}],"id":[{"id":"10.13039\/100017146","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["UF130329"],"award-info":[{"award-number":["UF130329"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000288","name":"Royal Society","doi-asserted-by":"publisher","award":["URF\\R\\191006"],"award-info":[{"award-number":["URF\\R\\191006"]}],"id":[{"id":"10.13039\/501100000288","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000835","name":"University of Bath","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/501100000835","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/P020194\/1"],"award-info":[{"award-number":["EP\/P020194\/1"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/R029431"],"award-info":[{"award-number":["EP\/R029431"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/S003053\/1"],"award-info":[{"award-number":["EP\/S003053\/1"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/T022078\/1"],"award-info":[{"award-number":["EP\/T022078\/1"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/na","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/X035859"],"award-info":[{"award-number":["EP\/X035859"]}],"id":[{"id":"10.13039\/na","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,14]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Lithium-rich cathode materials offer significantly higher energy densities than conventional cathode materials, due to their ability to store charge beyond the formal transition-metal redox limit, via so-called \u201coxygen redox\u201d. In lithium-rich oxides, oxygen redox is accompanied by molecular O2 formation and transition-metal migration, associated with irreversible structural change and poor cycling stability. Lithium-rich silicates provide an alternative lithium-rich chemistry, and have been proposed to be resilient to O2 formation at the top of charge, due to their covalently bonded [SiO4]4\u2212 framework. We report a computational study of the top-of-charge behavior of the prototypical silicate cathode Li2FeSiO4. Using density functional theory, we predict that fully delithiated FeSiO4 is thermodynamically unstable with respect to oxidation of oxide ions to form molecular O2 within the bulk material. Ab initio molecular dynamics shows this decomposition occurs spontaneously, via a multistep mechanism involving FeIV migration and disproportionation to FeIII and FeV, and subsequent FeV reduction alongside molecular O2 formation. Our findings demonstrate that polyanionic frameworks do not inherently prevent O2 formation in lithium-rich cathodes, and illustrate how different previously proposed oxygen redox mechanisms can function as steps within a compound process.<\/jats:p>","DOI":"10.1021\/jacs.6c02850","type":"journal-article","created":{"date-parts":[[2026,9,28]],"date-time":"2026-09-28T21:01:48Z","timestamp":1790629308000},"page":"42928-42938","source":"Crossref","is-referenced-by-count":0,"title":["Multi-Step Oxygen Redox\nMechanism in the Polyanionic\nLithium-Rich Cathode Li2FeSiO4"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-6511-6442","authenticated-orcid":true,"given":"Patrick J.","family":"Taylor","sequence":"first","affiliation":[{"name":"University of Bath , , ,","place":["Claverton Down, Bath, U.K., BA2 7AY"]},{"name":"The Faraday Institution , Quad One, Harwell Science and Innovation Campus , ,","place":["Didcot, U.K., OX11 0RA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kit","family":"McColl","sequence":"additional","affiliation":[{"name":"University of Bath , , ,","place":["Claverton Down, Bath, U.K., BA2 7AY"]},{"name":"The Faraday Institution , Quad One, Harwell Science and Innovation Campus , ,","place":["Didcot, U.K., OX11 0RA"]},{"name":"University of Oxford , , ,","place":["Oxford, U.K., OX2 6NN"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3882-0285","authenticated-orcid":true,"given":"M. Saiful","family":"Islam","sequence":"additional","affiliation":[{"name":"The Faraday Institution , Quad One, Harwell Science and Innovation Campus , ,","place":["Didcot, U.K., OX11 0RA"]},{"name":"University of Oxford , , ,","place":["Oxford, U.K., OX2 6NN"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3056-8233","authenticated-orcid":true,"given":"Benjamin J.","family":"Morgan","sequence":"additional","affiliation":[{"name":"University of Bath , , ,","place":["Claverton Down, Bath, U.K., BA2 7AY"]},{"name":"The Faraday Institution , Quad One, Harwell Science and Innovation Campus , ,","place":["Didcot, U.K., OX11 0RA"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,28]]},"reference":[{"key":"2026101414070437800_cit1","volume-title":"Global\nEV Outlook 2023, Tech. Rep.","year":"2023"},{"key":"2026101414070437800_cit2","doi-asserted-by":"publisher","first-page":"373","DOI":"10.1038\/s41560-018-0097-0","article-title":"Fundamental understanding and practical challenges\nof anionic redox activity in Li-ion batteries","volume":"3","author":"Assat","year":"2018","journal-title":"Nat. Energy"},{"key":"2026101414070437800_cit3","doi-asserted-by":"publisher","first-page":"522","DOI":"10.1038\/s41578-022-00416-1","article-title":"Pushing the limit\nof 3d transition metal-based layered oxides that use both cation and\nanion redox for energy storage","volume":"7","author":"Zhang","year":"2022","journal-title":"Nat. Rev. Mater."},{"key":"2026101414070437800_cit4","doi-asserted-by":"publisher","first-page":"345","DOI":"10.1039\/C9EE02803J","article-title":"Cation-disordered rocksalt\ntransition metal oxides\nand oxyfluorides for high energy lithium-ion cathodes","volume":"13","author":"Cle\u0301ment","year":"2020","journal-title":"Energy Environ. Sci."},{"key":"2026101414070437800_cit5","doi-asserted-by":"publisher","first-page":"781","DOI":"10.1038\/s41560-021-00780-2","article-title":"The role of O2 in O-redox\ncathodes for Li-ion batteries","volume":"6","author":"House","year":"2021","journal-title":"Nat. Energy"},{"key":"2026101414070437800_cit6","doi-asserted-by":"publisher","first-page":"4450","DOI":"10.1039\/D0EE01694B","article-title":"Li-rich cathodes\nfor rechargeable Li-based batteries: Reaction mechanisms and advanced\ncharacterization techniques","volume":"13","author":"Zuo","year":"2020","journal-title":"Energy Environ.\nSci."},{"key":"2026101414070437800_cit7","doi-asserted-by":"publisher","first-page":"A2490","DOI":"10.1149\/2.0111514jes","article-title":"Review\u2500Li-rich layered oxide cathodes for next-generation\nLi-ion batteries: Chances and challenges","volume":"162","author":"Rozier","year":"2015","journal-title":"J.\nElectrochem. Soc."},{"key":"2026101414070437800_cit8","doi-asserted-by":"publisher","first-page":"818","DOI":"10.1038\/s41563-024-01833-z","article-title":"Trapped O2 and the origin of voltage fade in layered Li-rich cathodes","volume":"23","author":"Marie","year":"2024","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit9","doi-asserted-by":"publisher","first-page":"826","DOI":"10.1038\/s41563-024-01873-5","article-title":"Phase segregation\nand nanoconfined fluid O2 in a lithium-rich oxide cathode","volume":"23","author":"McColl","year":"2024","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit10","doi-asserted-by":"publisher","first-page":"21799","DOI":"10.1021\/jacs.0c10270","article-title":"Redox chemistry\nand the role of trapped\nmolecular O2 in Li-rich disordered rocksalt oxyfluoride\ncathodes","volume":"142","author":"Sharpe","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"2026101414070437800_cit11","doi-asserted-by":"publisher","first-page":"5275","DOI":"10.1038\/s41467-022-32983-w","article-title":"Transition metal\nmigration and O2 formation underpin voltage hysteresis\nin oxygen-redox disordered rocksalt cathodes","volume":"13","author":"McColl","year":"2022","journal-title":"Nat. Commun."},{"key":"2026101414070437800_cit12","doi-asserted-by":"publisher","first-page":"214","DOI":"10.1038\/s41563-020-00816-0","article-title":"Cation-disordered\nrocksalt-type high-entropy cathodes for Li-ion batteries","volume":"20","author":"Lun","year":"2021","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit13","doi-asserted-by":"publisher","first-page":"8426","DOI":"10.1039\/D3TA00852E","article-title":"Recent progress and perspectives\non cation disordered rock-salt material for advanced Li-ion batteries","volume":"11","author":"Zhang","year":"2023","journal-title":"J. Mater. Chem. A"},{"key":"2026101414070437800_cit14","doi-asserted-by":"publisher","first-page":"223","DOI":"10.1021\/jacs.4c09070","article-title":"Oxygen dimerization-driven\ncation\nmigration induces voltage hysteresis in disordered rocksalt cathodes","volume":"147","author":"Kim","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026101414070437800_cit15","doi-asserted-by":"publisher","first-page":"2502766","DOI":"10.1002\/adma.202502766","article-title":"Disordered rocksalts as high-energy\nand earth-abundant Li-ion cathodes","volume":"37","author":"Hau","year":"2025","journal-title":"Adv. Mater."},{"key":"2026101414070437800_cit16","doi-asserted-by":"publisher","first-page":"20210017","DOI":"10.1002\/bte2.20210017","article-title":"Hysteresis in electrochemical\nsystems","volume":"1","author":"Van der Ven","year":"2022","journal-title":"Batt. Energy"},{"key":"2026101414070437800_cit17","doi-asserted-by":"publisher","first-page":"1369","DOI":"10.1016\/j.joule.2020.05.004","article-title":"Design\nrules for high-valent redox in intercalation electrodes","volume":"4","author":"Gent","year":"2020","journal-title":"Joule"},{"key":"2026101414070437800_cit18","doi-asserted-by":"publisher","first-page":"6656","DOI":"10.1021\/acs.chemmater.6b02870","article-title":"Lithium extraction\nmechanism in Li-rich Li2MnO3 involving oxygen\nhole formation and dimerization","volume":"28","author":"Chen","year":"2016","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit19","doi-asserted-by":"publisher","first-page":"777","DOI":"10.1038\/s41560-020-00697-2","article-title":"First-cycle voltage hysteresis in\nLi-rich 3d cathodes associated with molecular O2 trapped\nin the bulk","volume":"5","author":"House","year":"2020","journal-title":"Nat. Energy"},{"key":"2026101414070437800_cit20","doi-asserted-by":"publisher","first-page":"2091","DOI":"10.1038\/s41467-017-02041-x","article-title":"Coupling between oxygen redox and\ncation migration\nexplains unusual electrochemistry in lithium-rich layered oxides","volume":"8","author":"Gent","year":"2017","journal-title":"Nat. Commun."},{"key":"2026101414070437800_cit21","doi-asserted-by":"publisher","first-page":"156","DOI":"10.1016\/j.elecom.2004.11.008","article-title":"Electrochemical\nperformance of Li2FeSiO4 as a new Li-battery\ncathode material","volume":"7","author":"Nyte\u0301n","year":"2005","journal-title":"Electrochem. Commun."},{"key":"2026101414070437800_cit22","doi-asserted-by":"publisher","first-page":"9811","DOI":"10.1039\/c1jm10312a","article-title":"Silicate cathodes\nfor lithium batteries:\nAlternatives to phosphates?","volume":"21","author":"Islam","year":"2011","journal-title":"J. Mater. Chem."},{"key":"2026101414070437800_cit23","doi-asserted-by":"publisher","first-page":"172","DOI":"10.1016\/j.electacta.2013.07.190","article-title":"Insights into electrochemical performance\nof Li2FeSiO4 from first-principles calculations","volume":"111","author":"Zhang","year":"2013","journal-title":"Electrochim. Acta"},{"key":"2026101414070437800_cit24","doi-asserted-by":"publisher","first-page":"7314","DOI":"10.1039\/C4TA06305H","article-title":"In situ Fe K-edge\nX-ray absorption spectroscopy study during cycling of Li2FeSiO4 and Li2.2Fe0.9SiO4 Li ion battery materials","volume":"3","author":"Brownrigg","year":"2015","journal-title":"J. Mater. Chem.\nA"},{"key":"2026101414070437800_cit25","doi-asserted-by":"publisher","first-page":"10056","DOI":"10.1002\/anie.202100730","article-title":"Peroxo species formed in the bulk\nof silicate cathodes","volume":"60","author":"Chen","year":"2021","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026101414070437800_cit26","doi-asserted-by":"publisher","first-page":"692","DOI":"10.1038\/nchem.2524","article-title":"The structural\nand chemical origin of the oxygen redox activity in layered and cation-disordered\nLi-excess cathode materials","volume":"8","author":"Seo","year":"2016","journal-title":"Nat. Chem."},{"key":"2026101414070437800_cit27","doi-asserted-by":"publisher","first-page":"10068","DOI":"10.1021\/acs.jpclett.4c01929","article-title":"Topological protection\nof oxygen redox in Li-rich cathodes","volume":"15","author":"Chen","year":"2024","journal-title":"J. Phys.\nChem. Lett."},{"key":"2026101414070437800_cit28","doi-asserted-by":"publisher","first-page":"743","DOI":"10.1038\/s41563-025-02144-7","article-title":"Clarifying the origin\nof molecular O2 in cathode oxides","volume":"24","author":"Gao","year":"2025","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit29","doi-asserted-by":"publisher","DOI":"10.1002\/smtd.202501023","article-title":"The nature of oxidized\noxygen in oxygen redox cathodes","volume":"9","author":"Zhang","year":"2025","journal-title":"Small Methods"},{"key":"2026101414070437800_cit30","doi-asserted-by":"publisher","first-page":"1070","DOI":"10.1038\/s41557-021-00775-2","article-title":"Correlating ligand-to-metal charge\ntransfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting\nanionic redox","volume":"13","author":"Li","year":"2021","journal-title":"Nat. Chem."},{"key":"2026101414070437800_cit31","doi-asserted-by":"publisher","first-page":"1165","DOI":"10.1038\/s41563-022-01278-2","article-title":"Capturing dynamic\nligand-to-metal charge transfer with a long-lived cationic intermediate\nfor anionic redox","volume":"21","author":"Li","year":"2022","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit32","doi-asserted-by":"publisher","first-page":"720","DOI":"10.1016\/j.joule.2021.01.006","article-title":"Oxygen-redox reactions\nin LiCoO2 cathode\nwithout O\u2212O bonding during charge-discharge","volume":"5","author":"Hu","year":"2021","journal-title":"Joule"},{"key":"2026101414070437800_cit33","doi-asserted-by":"publisher","first-page":"684","DOI":"10.1038\/nchem.2471","article-title":"Charge-compensation\nin 3d-transition-metal-oxide\nintercalation cathodes through the generation of localized electron\nholes on oxygen","volume":"8","author":"Luo","year":"2016","journal-title":"Nat. Chem."},{"key":"2026101414070437800_cit34","doi-asserted-by":"publisher","first-page":"1908","DOI":"10.1021\/jacs.0c10704","article-title":"Delocalized metal\u2212oxygen \u03c0-redox\nis the origin of anomalous nonhysteretic capacity in Li-ion and Na-ion\ncathode materials","volume":"143","author":"Kitchaev","year":"2021","journal-title":"J. Am. Chem. Soc."},{"key":"2026101414070437800_cit35","doi-asserted-by":"publisher","first-page":"351","DOI":"10.1038\/s41560-023-01211-0","article-title":"Delocalized electron holes on oxygen in a battery cathode","volume":"8","author":"House","year":"2023","journal-title":"Nat. Energy"},{"key":"2026101414070437800_cit36","doi-asserted-by":"publisher","first-page":"496","DOI":"10.1038\/s41563-019-0318-3","article-title":"Unified picture of anionic redox in Li\/Na-ion batteries","volume":"18","author":"Ben Yahia","year":"2019","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit37","doi-asserted-by":"publisher","first-page":"256","DOI":"10.1038\/s41563-018-0276-1","article-title":"Metal\u2212oxygen\ndecoordination stabilizes anion redox in Li-rich oxides","volume":"18","author":"Hong","year":"2019","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit38","doi-asserted-by":"publisher","first-page":"639","DOI":"10.1038\/s41560-019-0439-6","article-title":"Manganese\noxidation as the origin of the anomalous capacity of Mn-containing\nLi-excess cathode materials","volume":"4","author":"Radin","year":"2019","journal-title":"Nat. Energy"},{"key":"2026101414070437800_cit39","doi-asserted-by":"publisher","first-page":"1625","DOI":"10.1021\/acs.chemmater.0c03734","article-title":"A two-step\noxidation mechanism controlled\nby Mn migration explains the first-cycle activation behavior of Li2MnO3-based Li-excess materials","volume":"33","author":"Vinckeviciute","year":"2021","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit40","doi-asserted-by":"publisher","first-page":"10206","DOI":"10.1021\/acs.jpcc.5b00362","article-title":"Crystal structural\nchanges and charge compensation mechanism during two lithium extraction\/insertion\nbetween Li2FeSiO4 and FeSiO4","volume":"119","author":"Masese","year":"2015","journal-title":"J. Phys. Chem. C"},{"key":"2026101414070437800_cit41","doi-asserted-by":"publisher","first-page":"6262","DOI":"10.1021\/acs.jpclett.8b02725","article-title":"Mechanism\nof exact transition between cationic and anionic redox activities\nin cathode material Li2FeSiO4","volume":"9","author":"Zheng","year":"2018","journal-title":"J. Phys. Chem. Lett."},{"key":"2026101414070437800_cit42","doi-asserted-by":"publisher","first-page":"22756","DOI":"10.1039\/D2CP00473A","article-title":"First principles\ninvestigation of anionic redox in bisulfate lithium battery cathodes","volume":"24","author":"Jha","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026101414070437800_cit43","doi-asserted-by":"publisher","first-page":"rl5ll","DOI":"10.26434\/chemrxiv-2023-rl5ll","article-title":"Accessing polyanionic\nredox in high voltage Li-rich thiophosphates","author":"Zarabadi-Poor","year":"2023","journal-title":"ChemRxiv"},{"key":"2026101414070437800_cit44","doi-asserted-by":"publisher","first-page":"217","DOI":"10.1016\/j.elecom.2005.11.010","article-title":"Structure and electrochemical\nperformance\nof Li2MnSiO4 and Li2FeSiO4 as potential Li-battery cathode materials","volume":"8","author":"Dominko","year":"2006","journal-title":"Electrochem. Commun."},{"key":"2026101414070437800_cit45","doi-asserted-by":"publisher","first-page":"495","DOI":"10.1021\/cm202818u","article-title":"Crystal structure, energetics,\nand electrochemistry of Li2FeSiO4 polymorphs\nfrom first principles calculations","volume":"24","author":"Saracibar","year":"2012","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit46","doi-asserted-by":"publisher","first-page":"9506","DOI":"10.1039\/c0jm03928d","article-title":"A novel Li2FeSiO4\/C composite: Synthesis, characterization\nand high storage capacity","volume":"21","author":"Lv","year":"2011","journal-title":"J. Mater. Chem."},{"key":"2026101414070437800_cit47","doi-asserted-by":"publisher","first-page":"109","DOI":"10.1016\/j.electacta.2016.12.008","article-title":"Novel insights into\nhigher capacity from the Li-ion battery cathode material Li2FeSiO4","volume":"223","author":"Liivat","year":"2017","journal-title":"Electrochim. Acta"},{"key":"2026101414070437800_cit48","doi-asserted-by":"publisher","first-page":"2155","DOI":"10.1021\/cm300749w","article-title":"Insights into changes\nin voltage and structure of Li2FeSiO4 polymorphs\nfor lithium-ion batteries","volume":"24","author":"Eames","year":"2012","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit49","doi-asserted-by":"publisher","first-page":"11169","DOI":"10.1103\/PhysRevB.54.11169","article-title":"Efficient iterative schemes for ab initio total-energy\ncalculations using a plane-wave basis set","volume":"54","author":"Kresse","year":"1996","journal-title":"Phys.\nRev. B: Condens. Matter Mater. Phys."},{"key":"2026101414070437800_cit50","doi-asserted-by":"publisher","first-page":"15","DOI":"10.1016\/0927-0256(96)00008-0","article-title":"Efficiency\nof ab-initio total energy calculations for\nmetals and semiconductors using a plane-wave basis set","volume":"6","author":"Kresse","year":"1996","journal-title":"Comput. Mater. Sci."},{"key":"2026101414070437800_cit51","doi-asserted-by":"publisher","first-page":"17953","DOI":"10.1103\/PhysRevB.50.17953","article-title":"Projector\naugmented-wave method","volume":"50","author":"Blo\u0308chl","year":"1994","journal-title":"Phys. Rev. B:Condens.\nMatter Mater. Phys."},{"key":"2026101414070437800_cit52","doi-asserted-by":"publisher","first-page":"1758","DOI":"10.1103\/PhysRevB.59.1758","article-title":"From ultrasoft pseudopotentials\nto the projector augmented-wave\nmethod","volume":"59","author":"Kresse","year":"1999","journal-title":"Phys. Rev. B: Condens. Matter Ma ter.\nPhys."},{"key":"2026101414070437800_cit53","doi-asserted-by":"publisher","first-page":"8208","DOI":"10.1021\/acs.jpclett.0c02405","article-title":"Accurate and\nnumerically efficient r2SCAN meta-generalized gradient\napproximation","volume":"11","author":"Furness","year":"2020","journal-title":"J. Phys. Chem. Lett."},{"key":"2026101414070437800_cit54","doi-asserted-by":"publisher","first-page":"075422","DOI":"10.1103\/PhysRevB.106.075422","article-title":"Workhorse\nminimally\nempirical dispersion-corrected density functional with tests for weakly\nbound systems: r2SCAN + rVV10","volume":"106","author":"Ning","year":"2022","journal-title":"Phys.\nRev. B"},{"key":"2026101414070437800_cit55","doi-asserted-by":"publisher","first-page":"1931","DOI":"10.1002\/jcc.26353","article-title":"LOBSTER: Local\norbital projections, atomic charges,\nand chemical-bonding analysis from projector-augmented-wave-based\ndensity-functional theory","volume":"41","author":"Nelson","year":"2020","journal-title":"J. Comput. Chem."},{"key":"2026101414070437800_cit56","doi-asserted-by":"publisher","first-page":"1030","DOI":"10.1002\/jcc.24300","article-title":"LOBSTER: A\ntool to extract chemical bonding from plane-wave based DFT","volume":"37","author":"Maintz","year":"2016","journal-title":"J. Comput. Chem."},{"key":"2026101414070437800_cit57","doi-asserted-by":"publisher","first-page":"165902","DOI":"10.1088\/1361-648X\/ab51ff","article-title":"Wannier90 as a community\ncode: New features and applications","volume":"32","author":"Pizzi","year":"2020","journal-title":"J. Phys.:\nCondens. Matter"},{"key":"2026101414070437800_cit58","doi-asserted-by":"publisher","first-page":"1463","DOI":"10.1021\/ct500985f","article-title":"Compressed\nrepresentation of Kohn\u2212Sham orbitals\nvia selected columns of the density matrix","volume":"11","author":"Damle","year":"2015","journal-title":"J. Chem. Theory Comput."},{"key":"2026101414070437800_cit59","doi-asserted-by":"publisher","first-page":"1392","DOI":"10.1137\/17M1129696","article-title":"Disentanglement via\nentanglement: A unified method for Wannier localization","volume":"16","author":"Damle","year":"2018","journal-title":"Multiscale Model. Simul."},{"key":"2026101414070437800_cit60","doi-asserted-by":"publisher","first-page":"011002","DOI":"10.1063\/1.4812323","article-title":"Commentary:\nThe Materials Project:\nA materials genome approach to accelerating materials innovation","volume":"1","author":"Jain","year":"2013","journal-title":"APL Mater."},{"key":"2026101414070437800_cit61","doi-asserted-by":"publisher","first-page":"314","DOI":"10.1016\/j.commatsci.2012.10.028","article-title":"Python materials genomics\n(pymatgen): A robust, open-source Python\nlibrary for materials analysis","volume":"68","author":"Ong","year":"2013","journal-title":"Comput. Mater.\nSci."},{"key":"2026101414070437800_cit62","doi-asserted-by":"publisher","first-page":"273002","DOI":"10.1088\/1361-648X\/aa680e","article-title":"The atomic simulation\nenvironment\u2500a Python library for working with atoms","volume":"29","author":"Larsen","year":"2017","journal-title":"J. Phys.: Condens. Matter"},{"key":"2026101414070437800_cit63","doi-asserted-by":"publisher","first-page":"1900015","DOI":"10.1002\/adts.201900015","article-title":"ICET \u2212 A Python\nlibrary for constructing and sampling alloy cluster expansions","volume":"2","author":"\u00c5ngqvist","year":"2019","journal-title":"Adv. Theory Simul."},{"key":"2026101414070437800_cit64","doi-asserted-by":"publisher","DOI":"10.5281\/zenodo.4460130","volume-title":"vasppy","author":"Morgan","year":"2021"},{"key":"2026101414070437800_cit65","doi-asserted-by":"publisher","first-page":"90","DOI":"10.1109\/MCSE.2007.55","article-title":"Matplotlib:\nA 2D graphics environment","volume":"9","author":"Hunter","year":"2007","journal-title":"Comput. Sci. Eng."},{"key":"2026101414070437800_cit66","doi-asserted-by":"publisher","first-page":"261","DOI":"10.1038\/s41592-019-0686-2","article-title":"SciPy 1.0: Fundamental algorithms for scientific computing\nin Python","volume":"17","author":"Virtanen","year":"2020","journal-title":"Nat. Methods"},{"key":"2026101414070437800_cit67","doi-asserted-by":"publisher","first-page":"357","DOI":"10.1038\/s41586-020-2649-2","article-title":"Array programming\nwith NumPy","volume":"585","author":"Harris","year":"2020","journal-title":"Nature"},{"key":"2026101414070437800_cit68","doi-asserted-by":"publisher","first-page":"1272","DOI":"10.1107\/S0021889811038970","article-title":"VESTA 3 for three-dimensional visualization of crystal, volumetric\nand morphology data","volume":"44","author":"Momma","year":"2011","journal-title":"J. Appl. Crystallogr."},{"key":"2026101414070437800_cit69","doi-asserted-by":"publisher","first-page":"13031","DOI":"10.1021\/ja2018543","article-title":"Structure\nand lithium\ntransport pathways in Li2FeSiO4 cathodes for\nlithium batteries","volume":"133","author":"Armstrong","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"2026101414070437800_cit71","doi-asserted-by":"publisher","first-page":"2266","DOI":"10.1039\/B601184E","article-title":"The lithium extraction\/insertion mechanism in Li2FeSiO4","volume":"16","author":"Nyte\u0301n","year":"2006","journal-title":"J. Mater. Chem."},{"key":"2026101414070437800_cit72","doi-asserted-by":"publisher","first-page":"133","DOI":"10.1038\/s41524-022-00818-3","article-title":"Approaches\nfor handling high-dimensional cluster expansions of ionic systems","volume":"8","author":"Yang","year":"2022","journal-title":"npj Comput. Mater."},{"key":"2026101414070437800_cit73","doi-asserted-by":"publisher","first-page":"043005","DOI":"10.1103\/PRXEnergy.2.043005","article-title":"Modeling intercalation\nchemistry with multiredox reactions by sparse lattice models in disordered\nrocksalt cathodes","volume":"2","author":"Zhong","year":"2023","journal-title":"PRX Energy"},{"key":"2026101414070437800_cit74","doi-asserted-by":"publisher","first-page":"7959","DOI":"10.1021\/acs.jpcc.1c00718","article-title":"Crystal orbital\nbond index: Covalent bond orders in solids","volume":"125","author":"Mu\u0308ller","year":"2021","journal-title":"J. Phys. Chem. C"},{"key":"2026101414070437800_cit75","doi-asserted-by":"publisher","first-page":"543","DOI":"10.1021\/cm0620943","article-title":"A first-principles\napproach to studying\nthe thermal stability of oxide cathode materials","volume":"19","author":"Wang","year":"2007","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit76","doi-asserted-by":"publisher","first-page":"qs91t","DOI":"10.26434\/chemrxiv-2024-qs91t","article-title":"Thermodynamically\nfavoured bulk O2 formation on charging in LiCoO2 and LiNiO2 cathode materials","author":"McColl","year":"2024","journal-title":"ChemRxiv"},{"key":"2026101414070437800_cit77","first-page":"123","article-title":"Refinement of the\nhematite structure","volume":"51","author":"Blake","year":"1966","journal-title":"Am. Mineral."},{"key":"2026101414070437800_cit78","doi-asserted-by":"publisher","first-page":"47911","DOI":"10.1021\/jacs.5c10485","article-title":"Decoding the\noxygen activity with iron through ligand-to-metal charge transfer\nin Li-rich layered cathodes","volume":"147","author":"Wang","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026101414070437800_cit79","doi-asserted-by":"publisher","first-page":"923","DOI":"10.1016\/0025-5408(77)90104-0","article-title":"Charge disproportionation\nin CaFeO3 studied with the Mo\u0308ssbauer effect","volume":"12","author":"Takano","year":"1977","journal-title":"Mater. Res. Bull."},{"key":"2026101414070437800_cit80","doi-asserted-by":"publisher","first-page":"2468","DOI":"10.1021\/acs.chemmater.2c00156","article-title":"Conversion of Li2FeSbO5 to the\nFe(III)\/Fe(V) phase LiFeSbO5 via topochemical lithium extraction","volume":"34","author":"Marti\u0301nez de Irujo-Labalde","year":"2022","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit81","doi-asserted-by":"publisher","first-page":"91","DOI":"10.1038\/s41563-025-02356-x","article-title":"A formal FeIII\/V redox couple in an intercalation\nelectrode","volume":"25","author":"Ramachandran","year":"2026","journal-title":"Nat. Mater."},{"key":"2026101414070437800_cit82","doi-asserted-by":"publisher","first-page":"5051","DOI":"10.1021\/cm502201z","article-title":"Differential electrochemical mass\nspectrometry study\nof the interface of xLi2MnO3\u00b7(1 \u2013 x)LiMO2 (M = Ni, Co, and Mn) material as a positive\nelectrode in Li-ion batteries","volume":"26","author":"Castel","year":"2014","journal-title":"Chem. Mater."},{"key":"2026101414070437800_cit83","doi-asserted-by":"crossref","unstructured":"Taylor, P. J.; McColl, K.; Islam, M. S.; Morgan, B. J.\n          Dataset for\n\u201cMulti-Step Oxygen Redox Mechanism\nin the Polyanionic Lithium-Rich Cathode Li2FeSiO4\u201d; University of Bath Research\nData Archive, 2026. 10.15125\/BATH-01647.","DOI":"10.26434\/chemrxiv.10001983\/v3"},{"key":"2026101414070437800_cit84","doi-asserted-by":"publisher","DOI":"10.5281\/zenodo.22919538","article-title":"Analysis Code and\nExtracted Data for \u201cMulti-step Oxygen Redox Mechanism in the\nPolyanionic Lithium-Rich Cathode Li2FeSiO4\u201d","author":"Taylor","year":"2026"}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c02850","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/40\/42928\/68682808\/jacs.6c02850.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/40\/42928\/68682808\/jacs.6c02850.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T18:14:32Z","timestamp":1792001672000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/40\/42928\/5440322\/Multi-Step-Oxygen-Redox-Mechanism-in-the"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,28]]},"references-count":83,"journal-issue":{"issue":"40","published-online":{"date-parts":[[2026,9,28]]},"published-print":{"date-parts":[[2026,10,14]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c02850","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.10001983\/v3","asserted-by":"object"}]},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,28]]}}}