[{"_id":"21040","publication_identifier":{"eissn":["2574-0962"]},"doi":"10.1021/acsaem.5c03511","article_type":"original","oa":1,"has_accepted_license":"1","year":"2026","publication_status":"published","file_date_updated":"2026-02-12T13:55:28Z","type":"journal_article","status":"public","quality_controlled":"1","page":"686-697","title":"Structural rearrangements of a Cobalt-free Lithium-rich layered oxide cathode during formation","intvolume":"         9","volume":9,"file":[{"file_name":"2026_AppliedEnergyMaterials_Busato.pdf","date_updated":"2026-02-12T13:55:28Z","content_type":"application/pdf","file_size":5977526,"date_created":"2026-02-12T13:55:28Z","checksum":"81272c19df41c696c1737168d3ea8c16","relation":"main_file","file_id":"21222","creator":"dernst","success":1,"access_level":"open_access"}],"article_processing_charge":"Yes (via OA deal)","month":"01","tmp":{"short":"CC BY (4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","image":"/images/cc_by.png","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)"},"day":"12","OA_type":"hybrid","scopus_import":"1","date_created":"2026-01-25T23:01:40Z","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.","OA_place":"publisher","publication":"ACS Applied Energy Materials","ddc":["540"],"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"}],"date_updated":"2026-02-12T14:04:04Z","department":[{"_id":"StFr"}],"PlanS_conform":"1","date_published":"2026-01-12T00:00:00Z","publisher":"American Chemical Society","issue":"1","language":[{"iso":"eng"}],"oa_version":"Published Version","citation":{"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>","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.","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>","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>.","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>.","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."},"acknowledged_ssus":[{"_id":"M-Shop"},{"_id":"LifeSc"}],"corr_author":"1","author":[{"full_name":"Busato, Matteo","first_name":"Matteo","last_name":"Busato"},{"full_name":"Tuccillo, Mariarosaria","first_name":"Mariarosaria","last_name":"Tuccillo"},{"first_name":"Arcangelo","last_name":"Celeste","full_name":"Celeste, Arcangelo"},{"first_name":"Alessandro","last_name":"Tofoni","full_name":"Tofoni, Alessandro"},{"full_name":"Silvestri, Laura","first_name":"Laura","last_name":"Silvestri"},{"full_name":"D’Angelo, Paola","first_name":"Paola","last_name":"D’Angelo"},{"orcid":"0000-0003-2902-5319","full_name":"Freunberger, Stefan Alexander","id":"A8CA28E6-CE23-11E9-AD2D-EC27E6697425","last_name":"Freunberger","first_name":"Stefan Alexander"},{"full_name":"Brutti, Sergio","last_name":"Brutti","first_name":"Sergio"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87"},{"citation":{"ieee":"R. B. Jethwa, D. Hey, R. N. Kerber, A. D. Bond, D. S. Wright, and C. P. Grey, “Exploring the landscape of heterocyclic quinones for redox flow batteries,” <i>ACS Applied Energy Materials</i>, vol. 7, no. 2. American Chemical Society, pp. 414–426, 2024.","chicago":"Jethwa, Rajesh B, Dominic Hey, Rachel N. Kerber, Andrew D. Bond, Dominic S. Wright, and Clare P. Grey. “Exploring the Landscape of Heterocyclic Quinones for Redox Flow Batteries.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2024. <a href=\"https://doi.org/10.1021/acsaem.3c02223\">https://doi.org/10.1021/acsaem.3c02223</a>.","ista":"Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. 2024. Exploring the landscape of heterocyclic quinones for redox flow batteries. ACS Applied Energy Materials. 7(2), 414–426.","mla":"Jethwa, Rajesh B., et al. “Exploring the Landscape of Heterocyclic Quinones for Redox Flow Batteries.” <i>ACS Applied Energy Materials</i>, vol. 7, no. 2, American Chemical Society, 2024, pp. 414–26, doi:<a href=\"https://doi.org/10.1021/acsaem.3c02223\">10.1021/acsaem.3c02223</a>.","ama":"Jethwa RB, Hey D, Kerber RN, Bond AD, Wright DS, Grey CP. Exploring the landscape of heterocyclic quinones for redox flow batteries. <i>ACS Applied Energy Materials</i>. 2024;7(2):414-426. doi:<a href=\"https://doi.org/10.1021/acsaem.3c02223\">10.1021/acsaem.3c02223</a>","short":"R.B. Jethwa, D. Hey, R.N. Kerber, A.D. Bond, D.S. Wright, C.P. Grey, ACS Applied Energy Materials 7 (2024) 414–426.","apa":"Jethwa, R. B., Hey, D., Kerber, R. N., Bond, A. D., Wright, D. S., &#38; Grey, C. P. (2024). Exploring the landscape of heterocyclic quinones for redox flow batteries. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.3c02223\">https://doi.org/10.1021/acsaem.3c02223</a>"},"language":[{"iso":"eng"}],"oa_version":"Published Version","user_id":"317138e5-6ab7-11ef-aa6d-ffef3953e345","author":[{"orcid":"0000-0002-0404-4356","full_name":"Jethwa, Rajesh B","first_name":"Rajesh B","last_name":"Jethwa","id":"4cc538d5-803f-11ed-ab7e-8139573aad8f"},{"full_name":"Hey, Dominic","last_name":"Hey","first_name":"Dominic"},{"first_name":"Rachel N.","last_name":"Kerber","full_name":"Kerber, Rachel N."},{"last_name":"Bond","first_name":"Andrew D.","full_name":"Bond, Andrew D."},{"full_name":"Wright, Dominic S.","first_name":"Dominic S.","last_name":"Wright"},{"last_name":"Grey","first_name":"Clare P.","full_name":"Grey, Clare P."}],"date_updated":"2025-09-04T11:36:32Z","department":[{"_id":"StFr"}],"abstract":[{"lang":"eng","text":"Redox flow batteries (RFBs) rely on the development of cheap, highly soluble, and high-energy-density electrolytes. Several candidate quinones have already been investigated in the literature as two-electron anolytes or catholytes, benefiting from fast kinetics, high tunability, and low cost. Here, an investigation of nitrogen-rich fused heteroaromatic quinones was carried out to explore avenues for electrolyte development. These quinones were synthesized and screened by using electrochemical techniques. The most promising candidate, 4,8-dioxo-4,8-dihydrobenzo[1,2-d:4,5-d′]bis([1,2,3]triazole)-1,5-diide (−0.68 V(SHE)), was tested in both an asymmetric and symmetric full-cell setup resulting in capacity fade rates of 0.35% per cycle and 0.0124% per cycle, respectively. In situ ultraviolet-visible spectroscopy (UV–Vis), nuclear magnetic resonance (NMR), and electron paramagnetic resonance (EPR) spectroscopies were used to investigate the electrochemical stability of the charged species during operation. UV–Vis spectroscopy, supported by density functional theory (DFT) modeling, reaffirmed that the two-step charging mechanism observed during battery operation consisted of two, single-electron transfers. The radical concentration during battery operation and the degree of delocalization of the unpaired electron were quantified with NMR and EPR spectroscopy."}],"ddc":["540"],"isi":1,"external_id":{"isi":["001146733200001"],"pmid":["38273966"]},"issue":"2","publisher":"American Chemical Society","date_published":"2024-01-22T00:00:00Z","article_processing_charge":"Yes (in subscription journal)","month":"01","volume":7,"file":[{"success":1,"access_level":"open_access","checksum":"2841e86a041d249ac0df2531b7f9aec1","date_created":"2024-07-16T11:59:24Z","relation":"main_file","file_id":"17262","creator":"dernst","date_updated":"2024-07-16T11:59:24Z","content_type":"application/pdf","file_size":5607177,"file_name":"2024_ACSAppElecMaterials_Jethwa.pdf"}],"intvolume":"         7","keyword":["Electrical and Electronic Engineering","Materials Chemistry","Electrochemistry","Energy Engineering and Power Technology","Chemical Engineering (miscellaneous)"],"project":[{"_id":"fc2ed2f7-9c52-11eb-aca3-c01059dda49c","call_identifier":"H2020","name":"IST-BRIDGE: International postdoctoral program","grant_number":"101034413"}],"page":"414-426","title":"Exploring the landscape of heterocyclic quinones for redox flow batteries","publication":"ACS Applied Energy Materials","scopus_import":"1","date_created":"2024-01-05T09:20:48Z","ec_funded":1,"tmp":{"short":"CC BY (4.0)","legal_code_url":"https://creativecommons.org/licenses/by/4.0/legalcode","image":"/images/cc_by.png","name":"Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)"},"pmid":1,"day":"22","has_accepted_license":"1","article_type":"original","oa":1,"_id":"14733","main_file_link":[{"url":"https://doi.org/10.1021/acsaem.3c02223","open_access":"1"}],"doi":"10.1021/acsaem.3c02223","publication_identifier":{"eissn":["2574-0962"]},"quality_controlled":"1","publication_status":"published","file_date_updated":"2024-07-16T11:59:24Z","year":"2024","status":"public","type":"journal_article"},{"title":"Influence of the ligand stripping on the transport properties of nanoparticle-based PbSe nanomaterials","page":"2120-2129","project":[{"_id":"260C2330-B435-11E9-9278-68D0E5697425","call_identifier":"H2020","grant_number":"754411","name":"ISTplus - Postdoctoral Fellowships"}],"intvolume":"         3","file":[{"file_name":"2020_ACSAppliedEnergyMat_Cadavid.pdf","content_type":"application/pdf","date_updated":"2022-08-23T08:34:17Z","file_size":6423548,"checksum":"f23be731a766a480c77c962c1380315c","date_created":"2022-08-23T08:34:17Z","file_id":"11942","creator":"dernst","relation":"main_file","success":1,"access_level":"open_access"}],"volume":3,"article_processing_charge":"No","month":"03","day":"01","ec_funded":1,"date_created":"2020-02-09T23:00:52Z","acknowledgement":"This work was supported by the Spanish Ministerio de Economía y Competitividad through the project SEHTOP (ENE2016-77798-C4-3-R) and the Generalitat de Catalunya through the project 2017SGR1246. D.C. acknowledges support from Universidad Nacional de Colombia. Y.L. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 754411. M.I. acknowledges financial support from IST Austria.","OA_type":"green","scopus_import":"1","publication":"ACS Applied Energy Materials","doi":"10.1021/acsaem.9b02137","publication_identifier":{"eissn":["2574-0962"]},"_id":"7467","oa":1,"article_type":"original","has_accepted_license":"1","status":"public","type":"journal_article","file_date_updated":"2022-08-23T08:34:17Z","publication_status":"published","year":"2020","quality_controlled":"1","oa_version":"Accepted Version","language":[{"iso":"eng"}],"citation":{"ieee":"D. Cadavid <i>et al.</i>, “Influence of the ligand stripping on the transport properties of nanoparticle-based PbSe nanomaterials,” <i>ACS Applied Energy Materials</i>, vol. 3, no. 3. American Chemical Society, pp. 2120–2129, 2020.","chicago":"Cadavid, Doris, Silvia Ortega, Sergio Illera, Yu Liu, Maria Ibáñez, Alexey Shavel, Yu Zhang, et al. “Influence of the Ligand Stripping on the Transport Properties of Nanoparticle-Based PbSe Nanomaterials.” <i>ACS Applied Energy Materials</i>. American Chemical Society, 2020. <a href=\"https://doi.org/10.1021/acsaem.9b02137\">https://doi.org/10.1021/acsaem.9b02137</a>.","mla":"Cadavid, Doris, et al. “Influence of the Ligand Stripping on the Transport Properties of Nanoparticle-Based PbSe Nanomaterials.” <i>ACS Applied Energy Materials</i>, vol. 3, no. 3, American Chemical Society, 2020, pp. 2120–29, doi:<a href=\"https://doi.org/10.1021/acsaem.9b02137\">10.1021/acsaem.9b02137</a>.","ista":"Cadavid D, Ortega S, Illera S, Liu Y, Ibáñez M, Shavel A, Zhang Y, Li M, López AM, Noriega G, Durá OJ, López De La Torre MA, Prades JD, Cabot A. 2020. Influence of the ligand stripping on the transport properties of nanoparticle-based PbSe nanomaterials. ACS Applied Energy Materials. 3(3), 2120–2129.","short":"D. Cadavid, S. Ortega, S. Illera, Y. Liu, M. Ibáñez, A. Shavel, Y. Zhang, M. Li, A.M. López, G. Noriega, O.J. Durá, M.A. López De La Torre, J.D. Prades, A. Cabot, ACS Applied Energy Materials 3 (2020) 2120–2129.","ama":"Cadavid D, Ortega S, Illera S, et al. Influence of the ligand stripping on the transport properties of nanoparticle-based PbSe nanomaterials. <i>ACS Applied Energy Materials</i>. 2020;3(3):2120-2129. doi:<a href=\"https://doi.org/10.1021/acsaem.9b02137\">10.1021/acsaem.9b02137</a>","apa":"Cadavid, D., Ortega, S., Illera, S., Liu, Y., Ibáñez, M., Shavel, A., … Cabot, A. (2020). Influence of the ligand stripping on the transport properties of nanoparticle-based PbSe nanomaterials. <i>ACS Applied Energy Materials</i>. American Chemical Society. <a href=\"https://doi.org/10.1021/acsaem.9b02137\">https://doi.org/10.1021/acsaem.9b02137</a>"},"author":[{"last_name":"Cadavid","first_name":"Doris","full_name":"Cadavid, Doris"},{"full_name":"Ortega, Silvia","first_name":"Silvia","last_name":"Ortega"},{"last_name":"Illera","first_name":"Sergio","full_name":"Illera, Sergio"},{"orcid":"0000-0001-7313-6740","full_name":"Liu, Yu","last_name":"Liu","first_name":"Yu","id":"2A70014E-F248-11E8-B48F-1D18A9856A87"},{"orcid":"0000-0001-5013-2843","full_name":"Ibáñez, Maria","first_name":"Maria","last_name":"Ibáñez","id":"43C61214-F248-11E8-B48F-1D18A9856A87"},{"last_name":"Shavel","first_name":"Alexey","full_name":"Shavel, Alexey"},{"last_name":"Zhang","first_name":"Yu","full_name":"Zhang, Yu"},{"full_name":"Li, Mengyao","first_name":"Mengyao","last_name":"Li"},{"first_name":"Antonio M.","last_name":"López","full_name":"López, Antonio M."},{"first_name":"Germán","last_name":"Noriega","full_name":"Noriega, Germán"},{"full_name":"Durá, Oscar Juan","last_name":"Durá","first_name":"Oscar Juan"},{"full_name":"López De La Torre, M. A.","last_name":"López De La Torre","first_name":"M. A."},{"full_name":"Prades, Joan Daniel","first_name":"Joan Daniel","last_name":"Prades"},{"last_name":"Cabot","first_name":"Andreu","full_name":"Cabot, Andreu"}],"user_id":"2DF688A6-F248-11E8-B48F-1D18A9856A87","isi":1,"external_id":{"isi":["000526598300012"]},"ddc":["540"],"abstract":[{"text":"Nanomaterials produced from the bottom-up assembly of nanocrystals may incorporate ∼1020–1021 cm–3 not fully coordinated surface atoms, i.e., ∼1020–1021 cm–3 potential donor or acceptor states that can strongly affect transport properties. Therefore, to exploit the full potential of nanocrystal building blocks to produce functional nanomaterials and thin films, a proper control of their surface chemistry is required. Here, we analyze how the ligand stripping procedure influences the charge and heat transport properties of sintered PbSe nanomaterials produced from the bottom-up assembly of colloidal PbSe nanocrystals. First, we show that the removal of the native organic ligands by thermal decomposition in an inert atmosphere leaves relatively large amounts of carbon at the crystal interfaces. This carbon blocks crystal growth during consolidation and at the same time hampers charge and heat transport through the final nanomaterial. Second, we demonstrate that, by stripping ligands from the nanocrystal surface before consolidation, nanomaterials with larger crystal domains, lower porosity, and higher charge carrier concentrations are obtained, thus resulting in nanomaterials with higher electrical and thermal conductivities. In addition, the ligand displacement leaves the nanocrystal surface unprotected, facilitating oxidation and chalcogen evaporation. The influence of the ligand displacement on the nanomaterial charge transport properties is rationalized here using a two-band model based on the standard Boltzmann transport equation with the relaxation time approximation. Finally, we present an application of the produced functional nanomaterials by modeling, fabricating, and testing a simple PbSe-based thermoelectric device with a ring geometry.","lang":"eng"}],"department":[{"_id":"MaIb"}],"date_updated":"2026-07-28T12:54:00Z","date_published":"2020-03-01T00:00:00Z","publisher":"American Chemical Society","issue":"3"}]