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Here, we use first-principles calculations to monitor the electronic and structural evolution of the spinel LiNi0.5Mn1.5O4 (LNMO) cathode at various stages of charge. In its P4332 ordered ground state, redox-active NiO6 octahedra are spatially isolated by redox-inactive Mn4+ cations, providing a clean platform to disentangle local redox and structural phenomena. By combining analyses of magnetic moments, Bader charges, and charge-density difference maps, we show that redox processes are localized on Ni, yet trigger significant transition metal\u2013oxygen rehybridization extending to both Ni\u2013O and Mn\u2013O networks. Changes in oxygen charge are traced to polarization driven by evolving Ni\u2013O bonding, rather than to anion redox activity. Concurrent structural changes include a stepwise volumetric contraction of the NiO6 octahedra with increasing oxidation state, and Jahn\u2013Teller distortions that are sensitively modulated by the local Li\/vacancy environment. Beyond these effects, we identify additional distortion modes, including pinching deformations in both NiO6 and MnO6 polyhedra, which exhibit clear and systematic trends with transition metal oxidation. Together, these results provide an atomic-level picture of coupled redox and lattice distortion processes in LNMO, revealing how Li\/vacancy configurations and transition metal\u2013oxygen rehybridization govern electrochemical behavior. The mechanisms uncovered here point to design principles that are likely to be equally critical in more complex oxide cathodes.<\/jats:p>","DOI":"10.1021\/jacs.6c05598","type":"journal-article","created":{"date-parts":[[2026,8,19]],"date-time":"2026-08-19T22:01:19Z","timestamp":1787176879000},"page":"36567-36582","source":"Crossref","is-referenced-by-count":1,"title":["Revealing the Structural-Redox\nInterplay in the High-Voltage\nSpinel LiNi0.5Mn1.5O4 Cathode"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0004-9665-9623","authenticated-orcid":true,"given":"Graciela E.","family":"Garci\u0301a Ponte","sequence":"first","affiliation":[{"name":"University of California Santa Barbara , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2144-4586","authenticated-orcid":true,"given":"Sesha Sai","family":"Behara","sequence":"additional","affiliation":[{"name":"University of California Santa Barbara , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3611-1162","authenticated-orcid":true,"given":"Raphae\u0308le J.","family":"Cle\u0301ment","sequence":"additional","affiliation":[{"name":"University of California Santa Barbara , , , ,","place":["Santa Barbara, California, United States, 93106"]},{"name":"University of California Santa Barbara , , , ,","place":["Santa Barbara, California, United States, 93106"]},{"name":"Max Planck Institute for Solid State Research , , ,","place":["Stuttgart, Germany, 70569"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anton","family":"Van der Ven","sequence":"additional","affiliation":[{"name":"University of California Santa Barbara , , , ,","place":["Santa Barbara, California, United States, 93106"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,19]]},"reference":[{"key":"2026090312103858600_cit1","doi-asserted-by":"publisher","first-page":"26","DOI":"10.1038\/s41560-019-0513-0","article-title":"High-nickel layered oxide cathodes\nfor lithium-based automotive batteries","volume":"5","author":"Li","year":"2020","journal-title":"Nat.\nEnergy"},{"key":"2026090312103858600_cit2","doi-asserted-by":"publisher","first-page":"267","DOI":"10.1038\/s41560-018-0107-2","article-title":"Performance\nand cost of materials for lithium-based rechargeable automotive batteries","volume":"3","author":"Schmuch","year":"2018","journal-title":"Nat. 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Mater."},{"key":"2026090312103858600_cit29","doi-asserted-by":"publisher","first-page":"664","DOI":"10.1038\/s41563-022-01209-1","article-title":"Coupling\nstructural evolution and oxygen-redox electrochemistry in\nlayered transition metal oxides","volume":"21","author":"Eum","year":"2022","journal-title":"Nat. Mater."},{"key":"2026090312103858600_cit30","doi-asserted-by":"crossref","DOI":"10.1017\/CBO9781139096782","volume-title":"Transition Metal Compounds","author":"Khomskii","year":"2014"},{"key":"2026090312103858600_cit31","doi-asserted-by":"publisher","first-page":"2992","DOI":"10.1021\/acs.chemrev.0c00579","article-title":"Orbital effects in solids: Basics, recent progress,\nand opportunities","volume":"121","author":"Khomskii","year":"2021","journal-title":"Chem. 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Mater."},{"key":"2026090312103858600_cit40","doi-asserted-by":"publisher","first-page":"2240","DOI":"10.1002\/cssc.201900032","article-title":"Phase transformation\nbehavior and stability of LiNiO2 cathode material for Li-ion\nbatteries obtained from in situ gas analysis and operando X-ray diffraction","volume":"12","author":"De Biasi","year":"2019","journal-title":"ChemSusChem"},{"key":"2026090312103858600_cit41","doi-asserted-by":"publisher","first-page":"090535","DOI":"10.1149\/1945-7111\/ac24ba","article-title":"Correlating cation mixing with Li\nkinetics: electrochemical\nand Li diffusion measurements on Li-deficient LiNiO2 and\nLi-excess LiNi0.5Mn0.5O2","volume":"168","author":"Phattharasupakun","year":"2021","journal-title":"J. Electrochem. Soc."},{"key":"2026090312103858600_cit42","doi-asserted-by":"publisher","first-page":"156","DOI":"10.1016\/j.jpowsour.2017.08.027","article-title":"A new design of highly\nreversible LiNiO2: Defect formation in transition metal\nsite","volume":"364","author":"Kobayashi","year":"2017","journal-title":"J. Power Sources"},{"key":"2026090312103858600_cit43","doi-asserted-by":"publisher","first-page":"10434","DOI":"10.1002\/anie.201812472","article-title":"There and back again\u2500the\njourney of LiNiO2 as a\ncathode active material","volume":"58","author":"Bianchini","year":"2019","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026090312103858600_cit44","doi-asserted-by":"publisher","first-page":"1802586","DOI":"10.1002\/aenm.201802586","article-title":"Kinetic stability\nof bulk LiNiO2 and surface degradation by oxygen evolution\nin LiNiO2-Based cathode materials","volume":"9","author":"Kong","year":"2019","journal-title":"Adv. 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Solid\nState Electrochem."},{"key":"2026090312103858600_cit48","doi-asserted-by":"publisher","first-page":"32","DOI":"10.1016\/j.ssi.2011.04.007","article-title":"A comparative study of Fd-3m and\nP4332 \u201cLiNi0.5Mn1.5O4\u201d","volume":"193","author":"Wang","year":"2011","journal-title":"Solid State Ionics"},{"key":"2026090312103858600_cit49","doi-asserted-by":"publisher","first-page":"1339","DOI":"10.1039\/c3ee42981d","article-title":"A perspective on\nthe high-voltage\nLiMn1.5Ni0.5O4 spinel cathode for\nlithium-ion batteries","volume":"7","author":"Manthiram","year":"2014","journal-title":"Energy Environ. Sci."},{"key":"2026090312103858600_cit50","doi-asserted-by":"publisher","first-page":"906","DOI":"10.1021\/cm035050s","article-title":"Comparative\nstudy of LiNi0.5Mn1.5O4-\u03b4 and LiNi0.5Mn1.5O4 cathodes having\ntwo crystallographic structures: Fd3\u0305m and P4332","volume":"16","author":"Kim","year":"2004","journal-title":"Chem. 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