Five-Dimensional Incommensurate Structure of the Melilite Electrolyte [CaNd]2[Ga]2[Ga2O7]2

• Main Authors: Wei, Fengxia, Baikie, Tom, An, Tao, Schreyer, Martin, Kloc, Christian, White, Timothy John
• Other Authors: School of Materials Science & Engineering
• Format: Article
• Language: English
• Published: 2017
• Subjects: Transmission electron microscopy; Electrolytes
• Online Access: https://hdl.handle.net/10356/85606; http://hdl.handle.net/10220/43745
• Institution: Nanyang Technological University

Melilite-type gallium oxides are potential intermediate temperature electrolytes for solid oxide fuel cells. Single crystals of [CaNd]2[Ga]2[Ga2O7]2 grown using an optical floating zone furnace have been investigated using transmission electron microscopy and powder and single-crystal X-ray diffraction. The anion array topologically conforms to a [(3.5.4.5)2, 3.5.3.5] network that contains distorted pentagonal tunnels. The distortion is necessary to achieve space filling and accommodate structural misfit between the layers. Satisfactory bond lengths and angles are obtained through two-dimensional modulation in the tetragonal based plane, leading to five-dimensional symmetry in the superspace group P4̅21m(α,α,0)00s(α̅a̅,a,0)000, α = 0.2319(2), with modulation vectors q1 = α(a* + b*) and q2 = α(−a* + b*). Both displacive and occupational modulations are found. Through this mechanism, melilites are primed to accommodate mobile oxygen interstitials, suggesting a rational approach to crystallochemical tailoring that will enhance ionic diffusion and optimize electrolyte performance.