Disorder and Oxide Ion Diffusion Mechanism in La(1.54)Sr(0.46)Ga(3)O(7.27) Melilite from Nuclear Magnetic Resonance

[Image: see text] Layered tetrahedral network melilite is a promising structural family of fast ion conductors that exhibits the flexibility required to accommodate interstitial oxide anions, leading to excellent ionic transport properties at moderate temperatures. Here, we present a combined experimental and computational magic angle spinning (MAS) nuclear magnetic resonance (NMR) approach which aims at elucidating the local configurational disorder and oxide ion diffusion mechanism in a key member of this structural family possessing the La(1.54)Sr(0.46)Ga(3)O(7.27) composition. (17)O and (71)Ga MAS NMR spectra display complex spectral line shapes that could be accurately predicted using a computational ensemble-based approach to model site disorder across multiple cationic and anionic sites, thereby enabling the assignment of bridging/nonbridging oxygens and the identification of distinct gallium coordination environments. The (17)O and (71)Ga MAS NMR spectra of La(1.54)Sr(0.46)Ga(3)O(7.27) display additional features not observed for the parent LaSrGa(3)O(7) phase which are attributed to interstitial oxide ions incorporated upon cation doping and stabilized by the formation of five-coordinate Ga centers conferring framework flexibility. (17)O high-temperature (HT) MAS NMR experiments capture exchange within the bridging oxygens at 130 °C and reveal coalescence of all oxygen signals in La(1.54)Sr(0.46)Ga(3)O(7.27) at approximately 300 °C, indicative of the participation of both interstitial and framework oxide ions in the transport process. These results further supported by the coalescence of the (71)Ga resonances in the (71)Ga HT MAS NMR spectra of La(1.54)Sr(0.46)Ga(3)O(7.27) unequivocally provide evidence of the conduction mechanism in this melilite phase and highlight the potential of MAS NMR spectroscopy to enhance the understanding of ionic motion in solid electrolytes.