title: Five-dimensional incommensurate structure of the melilite electrolyte [CaNd]2[Ga]2[Ga2O7]2.
abstract: Melilite-type gallium oxides are potential intermediate temperature electrolytes for solid oxide fuel cells. Single crystals of [CaNd](2)[Ga](2)[Ga(2)O(7)](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 P(4⁻)2(1)m(α,α,0)00s((a⁻)a,0)000, α = 0.2319(2), with modulation vectors q(1) = α(a* + b*) and q(2) = 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.
authors.affiliation: Division of Materials Science & Engineering, Nanyang Technological University, Singapore.
authors.forename: Fengxia
authors.initials: F
authors.lastname: Wei
authors.forename: Tom
authors.initials: T
authors.lastname: Baikie
authors.forename: Tao
authors.initials: T
authors.lastname: An
authors.forename: Martin
authors.initials: M
authors.lastname: Schreyer
authors.forename: Christian
authors.initials: C
authors.lastname: Kloc
authors.forename: Tim J
authors.initials: TJ
authors.lastname: White