La2Ga3O7.5: a metastable ternary melilite with a super-excess of inter- stitial oxide ions synthesized by direct crystallization of the melt
Résumé
The La1+xAE1-xGa3O7+x/2 melilite family (AE = Ca, Sr, Ba, and 0 < x < 0.64) demonstrates remarkable oxide ion conductivity due to the ability of its layered tetrahedral [Ga3O7+x/2] network to accommodate and transport interstitial oxide ions (Oint). Compositions x > 0.65 with very high Oint concentrations (referred to here as "super-excess" compositions) have the potential to support correspondingly high ionic conductivities, but have never before been accessed due to the limitations of conventional solid-state ceramic synthesis. Here we report that fully-substituted La2Ga3O7.5 (x = 1) melilite ceramics can be synthesized by direct crys-tallization of an under-cooled melt, demonstrating that super-excess compositions are accessible under suitable nonequilibrium reaction conditions. La2Ga3O7.5 is stable up to 830 °C and exhibits an ionic conductivity of 0.01 S.cm-1 at 800 °C, three orders of magnitude higher than the corresponding x = 0 end-member LaSrGa3O7, and close to the range exhibited by the current best-in-class La1.54Sr0.46Ga3O7.23 (0.1 S.cm-1). It crystallizes in an orthorhombic √2a x √2a x 2c expansion of the parent melilite cell, in space group Ima2, with full long-range ordering of Oint into chains within the [Ga3O7.5] layers. The emergence of this chain-like (1D) ordering within the 2D melilite framework, which appears to be an incipient feature of previously reported partially-ordered melilites, is explained in terms of the underlying hexagonal topology of the structure. These results will enable the exploration of extended com-positional ranges for the development of new solid oxide ion electrolytes with high concentrations of interstitial oxide charge carriers.
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