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Herein, we report the Li3N-assisted synthesis of the oxynitride La24Li23Ti5O53N3 (LLTON) and clarify the role of O\/N incorporation in defect reconstruction and Li-ion migration. Structure analyses reveal that nitrogen preferentially substitutes apical oxygen sites in Li\/Ti octahedra, inducing Li-site redistribution and oxygen-vacancy formation. These coupled defects reconstruct the local coordination environment and disrupt the ordered defect arrangement of the parent oxide while retaining the tetragonal framework. Variable-temperature diffraction further reveals a thermally driven structural evolution involving Li-site reorganization, enhanced positional disorder in the fluorite-related lithium sublattice, and a halving of the crystallographic repeat along the c direction. Ab initio molecular dynamics (AIMD) and bond valence site energy (BVSE) calculations show that these defect-induced and thermally activated rearrangements lower the Li-ion migration barrier and promote preferential one-dimensional migration along the c direction. Consequently, LLTON delivers an ionic conductivity of 3.78 mS cm\u20131 at 400 \u00b0C, with the activation energy reduced from 0.88 to 0.67 eV. This work establishes a structure\u2013defect\u2013evolution\u2013transport correlation in mixed-anion oxides and highlights O\/N defect engineering as a useful approach for regulating ion migration in complex oxide materials.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c03393","type":"journal-article","created":{"date-parts":[[2026,8,8]],"date-time":"2026-08-08T16:01:54Z","timestamp":1786204914000},"page":"19601-19611","source":"Crossref","is-referenced-by-count":0,"title":["O\/N Mixed-Anion\nDefect Engineering Mediates Structural\nEvolution and Li-ion Transport in La24Li23Ti5O53N3"],"prefix":"10.1021","volume":"65","author":[{"given":"Shi-Rui","family":"Zhang","sequence":"first","affiliation":[{"name":"Shaanxi Normal University , , ,","place":["Xi\u2019an, Shaanxi Province, P. R. 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