Publication date: 10th April 2024
Conductivity degradation is one of the key limitations in the commercial implementation of doped zirconia electrolytes. This closely aligns with odering phenomena in both the anion and cation lattices. We briefly review these phenomena and illustrate this with a special example, a magnesia and india co-doped zirconia composition that exhibits an unusual conductivity degradation-recovery profile where the conductivity degrades for a short period of time then recovers and exceeds its initial value. The conductivity at 850 °C in air was found recovered to the initial value of 0.096 S cm-1 in less than 25 hours, and then it continues to improve up to 0. 11 S cm-1 after 250 hours. This special behaviour in a stable single-phased composition allows us to unambiguously correlate conductivity changes over time to changes in short-range structure. Through a detailed structural characterisation by electron diffraction, TOF neutron diffraction and other techniques, the long-standing recognition that the conductivity degradation is related to short-range ordering is confirmed experimentally. We conclude that the conductivity degradation is caused by pyrochlore and rare-earth C-type ordering within the fluorite, whereas the conductivity increase and stabilisation observed in this composition is a result of eliminating such defect short-range ordering and moving towards a stable disordered fluorite structures.
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