20.500.12556/RUL-189583 Impact of chelating agent choice on growth kinetics and defect chemistry in sol–gel-synthesized Li- and Mn-rich layered cathodes The electrochemical performance and structural stability of Li- and Mn-rich layered oxide cathodes are critically influenced by synthesis conditions, yet the roles of chelating agents and defect chemistry remains elusive. In this study, we systematically investigate Li$_{1.2}$Mn$_{0.54}$Ni$_{0.13}$Co$_{0.13}$O$_{2}$ cathode powders synthesized via the sol−gel method using citric acid or oxalic acid as the chelating agent, each calcined at 850 and 900 °C. Despite introducing greater initial disorder, oxalic acid-derived samples, particularly the one calcined at 900 °C, demonstrate improved electrochemical stability and capacity retention. Operando XRD reveals that this material undergoes a pronounced unit cell expansion during the first cycle, a response linked largely to the mobility and homogenization of oxygen vacancies introduced during the synthesis. This structural flexibility accommodates redox-driven strain during cycling, which limits Li/TM mixing and enables over-reduction of Ni, as confirmed by operando XANES and ex situ EXAFS. These results highlight that oxygen vacancy mobility during cycling dominates the effects of the initial structural order, where different types of defects are present, and plays a decisive role in governing redox pathways and cycling stability. The selection of the precursor allows tailoring introduction of these defects without postsynthesis treatment. This study provides a comprehensive framework for designing high-performance Li- and Mn-rich layered oxide cathodes by tuning synthesis chemistry to engineer beneficial structural disorder and defect dynamics. Li-rich layered oxides Mn-rich layered oxides oxygen vacancies stacking faults chelating agents redox behavior cathode design Li-ion batteries oxides oxygen redox reactions defects in solids electrodes elektrokemija litijionske baterije oksidi katode true false true Angleški jezik Slovenski jezik Članek v reviji 2026-10-09 12:53:37 2026-10-09 12:53:39 2026-10-10 04:29:39 0000-00-00 00:00:00 2026 0 0 Str. 16268–16281 iss. 11 Vol. 18 2026 0000-00-00 Zaloznikova Objavljeno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 544.5/.6 1944-8252 10.1021/acsami.5c19987 274280451 impact-of-chelating-agent-choice-on-growth-kinetics-and-defect-chemistry-in-sol-gel-synthesized-li-and-mn-rich-layered.pdf impact-of-chelating-agent-choice-on-growth-kinetics-and-defect-chemistry-in-sol-gel-synthesized-li-and-mn-rich-layered.pdf 1 1D6937139DC9BC0A39C5247B5E0504BD 0e3da0485f710ccc3ca86118755b6d2e236d6beb0b554127b67df0ffe8533a9b de600229-c3cf-11f1-8bc5-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=250238 https://pubs.acs.org/aamick/article/18/11/16268/5077146/Impact-of-Chelating-Agent-Choice-on-Growth 0 d0c12654-c3cf-11f1-8bc5-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=250237 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0