{"OA_place":"publisher","language":[{"iso":"eng"}],"author":[{"last_name":"Busato","first_name":"Matteo","full_name":"Busato, Matteo"},{"first_name":"Mariarosaria","full_name":"Tuccillo, Mariarosaria","last_name":"Tuccillo"},{"first_name":"Arcangelo","full_name":"Celeste, Arcangelo","last_name":"Celeste"},{"last_name":"Tofoni","first_name":"Alessandro","full_name":"Tofoni, Alessandro"},{"full_name":"Silvestri, Laura","first_name":"Laura","last_name":"Silvestri"},{"last_name":"D’Angelo","first_name":"Paola","full_name":"D’Angelo, Paola"},{"first_name":"Stefan Alexander","orcid":"0000-0003-2902-5319","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","last_name":"Freunberger"},{"last_name":"Brutti","full_name":"Brutti, Sergio","first_name":"Sergio"}],"file":[{"content_type":"application/pdf","file_size":5977526,"creator":"dernst","access_level":"open_access","date_updated":"2026-02-12T13:55:28Z","file_id":"21222","success":1,"checksum":"81272c19df41c696c1737168d3ea8c16","file_name":"2026_AppliedEnergyMaterials_Busato.pdf","date_created":"2026-02-12T13:55:28Z","relation":"main_file"}],"publication_status":"published","type":"journal_article","intvolume":"         9","year":"2026","corr_author":"1","publisher":"American Chemical Society","user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","doi":"10.1021/acsaem.5c03511","oa_version":"Published Version","date_published":"2026-01-12T00:00:00Z","day":"12","issue":"1","tmp":{"short":"CC BY (4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)","image":"/images/cc_by.png"},"title":"Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation","article_processing_charge":"Yes (via OA deal)","PlanS_conform":"1","publication_identifier":{"eissn":["2574-0962"]},"_id":"21040","publication":"ACS Applied Energy Materials","department":[{"_id":"StFr"}],"acknowledged_ssus":[{"_id":"M-Shop"},{"_id":"LifeSc"}],"date_created":"2026-01-25T23:01:40Z","volume":9,"oa":1,"ddc":["540"],"OA_type":"hybrid","acknowledgement":"Elettra-Sincrotrone Trieste S.C.p.A. and its staff are acknowledged for providing synchrotron radiation beamtime and laboratory facilities, in particular the MCX and XAFS beamlines, where the XRD and XAS experiments have been carried out, supported by the projects number: 20217082, 20205109, and 20195014. This study was carried out within the MOST─Sustainable Mobility Center and received funding from the European Union Next-Generation EU (PIANO NAZIONALE DI RIPRESA E RESILIENZA (PNRR)─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.4─D.D. 1033 17/06/2022, CN00000023). Moreover, the contribution of S.B. and A.C. to this study was carried out within the NEST─Network for Energy Sustainable Transition and received funding from the European Union Next-Generation EU (PNRR─MISSIONE 4 COMPONENTE 2, INVESTIMENTO 1.3─D.D. 1561 11/10/2022, B53C22004070006). This manuscript reflects only the authors’ views and opinions, neither the European Union nor the European Commission can be considered responsible for them. Two of us, S.B. and S.A.F., would like to thank the Alistore ERI. L.S. received funds from the Ministry of Ecological Transition in the “Ricerca di Sistema Elettrico” framework. S.A.F. is indebted to ISTA for support. The Scientific Service Units of ISTA supported this research through resources provided by the Lab Support Facility and the Miba Machine Shop.","month":"01","has_accepted_license":"1","article_type":"original","quality_controlled":"1","status":"public","abstract":[{"text":"Formation during the first cycles of Li-rich layered oxide (LRLO) cathode materials consolidates the interphase and leads to structural changes that are decisive for long-term cyclability. However, the nature and effect of the changes are material-dependent and unknown for the important class of Co-free, Ni-poor LRLOs. Here, we analyze the processes during the tailored formation procedure of a typical class member, Li1.28Ni0.15Mn0.57O2, and demonstrate that it remarkably changes lattice composition and structure as a prerequisite for stable cycling. We combine electrochemistry, operando mass spectrometry, X-ray diffraction, and X-ray absorption spectroscopy with density functional theory simulations. Activation most prominently compresses the layer spacing along the c-axis and increases reversible structural breathing. The large capacity of ∼250 mAh g–1 originates from the Ni2+/Ni4+ and O2–/O– redox couples. Electron exchange during O-redox is smeared over the entire anionic sublattice rather than localized on specific oxygen atomic sites. This redox mechanism is reversible without detrimental oxygen evolution, avoiding continued degradation common in conventional LRLOs. Sequential Ni- and O-redox during activation irreversibly distorts the coordination of the redox-inactive Mn4+ centers. This structural evolution of the MnO6 octahedra appears to enable the superior electrochemical performance of this LRLO phase. These findings define an activation pathway for the important class of Co-free, Ni-poor LRLOs, offering potential guidance for the rational design of high-performance, more sustainable cathode materials.","lang":"eng"}],"page":"686-697","date_updated":"2026-02-12T14:04:04Z","citation":{"ista":"Busato M, Tuccillo M, Celeste A, Tofoni A, Silvestri L, D’Angelo P, Freunberger SA, Brutti S. 2026. Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. ACS Applied Energy Materials. 9(1), 686–697.","chicago":"Busato, Matteo, Mariarosaria Tuccillo, Arcangelo Celeste, Alessandro Tofoni, Laura Silvestri, Paola D’Angelo, Stefan Alexander Freunberger, and Sergio Brutti. “Structural Rearrangements of a Cobalt-Free Lithium-Rich Layered Oxide Cathode during Formation.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2026. <a href=\"https://doi.org/10.1021/acsaem.5c03511\">https://doi.org/10.1021/acsaem.5c03511</a>.","ama":"Busato M, Tuccillo M, Celeste A, et al. Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>. 2026;9(1):686-697. doi:<a href=\"https://doi.org/10.1021/acsaem.5c03511\">10.1021/acsaem.5c03511</a>","short":"M. Busato, M. Tuccillo, A. Celeste, A. Tofoni, L. Silvestri, P. D’Angelo, S.A. Freunberger, S. Brutti, ACS Applied Energy Materials 9 (2026) 686–697.","apa":"Busato, M., Tuccillo, M., Celeste, A., Tofoni, A., Silvestri, L., D’Angelo, P., … Brutti, S. (2026). Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.5c03511\">https://doi.org/10.1021/acsaem.5c03511</a>","ieee":"M. Busato <i>et al.</i>, “Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation,” <i>ACS Applied Energy Materials</i>, vol. 9, no. 1. American Chemical Society, pp. 686–697, 2026.","mla":"Busato, Matteo, et al. “Structural Rearrangements of a Cobalt-Free Lithium-Rich Layered Oxide Cathode during Formation.” <i>ACS Applied Energy Materials</i>, vol. 9, no. 1, American Chemical Society, 2026, pp. 686–97, doi:<a href=\"https://doi.org/10.1021/acsaem.5c03511\">10.1021/acsaem.5c03511</a>."},"file_date_updated":"2026-02-12T13:55:28Z","scopus_import":"1"}