We describe the measurement of electronic conductivity of solid oxide electrolytes by a modified Hebb-Wagner technique based on the use of blocking microelectrodes. Results are presented for a couple of typical solid oxide electrolyte systems mainly derived from ceria and lanthanum gallate. The examples demonstrate a good resolution of the microelectrode technique in particular within the electrolyte domain, i.e. around the minimum of the electronic conductivity. This made possible the detection of deviations from the predicted oxygen partial pressure dependence of simple defect models for the concentrations of electrons and holes. The observed deviations from these defect models, at least partially, reflect the overemphasized ideality of the usually applied semiconductor model.Whereas the effect of dissolved transition metals with variable valence states such as Fe, and Co on the electronic conduction is well known, it was unexpected to find a strong concentration dependent effect of dopants like Y 3+ and Zr 4+ in ceria or Mg 2+ and Sr 2+ in the gallates upon the electronic conductivity within the electrolytic domain. Ions like Y 3+ and Zr 4+ cause a shift and a partial broadening of electronic states in ceria based materials. Indications have been found for band tailing due to high defect concentrations. In some cases, the dopants cause the appearance of additional localized electron states in the gap which give rise to weak superimposed maxima of the electronic conductivity at a particular oxygen partial pressure within the electrolytic domain.Accordingly, one cannot expect that electronic conductivities of solid electrolytes are insensitive to a changing concentration of stabilizers such as Y, Ca, etc. For instance, even a moderate doping of ceria by zirconia leads to a considerable electronic excess conductivity in the electrolytic domain.

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