Abstract
Possible charge compensation models for the excess conducting Na+ ions in β‐alumina have been investigated with potential energy calculations. The cases studied include an artificial transfer of charge from Al3+ ions in the spinel block to Na+ ions in the conducting plane, the replacement of an Al3+ ion with three Na+ ions, the replacement of an Al3+ ion with a Mg2+ and a Na+ ion, and the interstitial oxygen model in which a VAl–Al–O–Al–VA1 defect compensates two extra Na+ ions. The results favor the last model.

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