Mechanism of electric conductivity change in BaCo0.7Fe0.2Nb0.1O3 − δ at intermediate temperature

•Change mechanism of conductivity in BCFN at intermediate temperature is studied.•The formation of oxygen vacancies results in the change of conductivity.•Gradually increased ion conductivity is caused by fully ionized oxygen vacancies.•Steady electric conductivity is explained by the blocking of Zerner exchange effect.

In this paper, the change mechanism of electric conductance behavior of BaCo0.7Fe0.2Nb0.1O3 − δ (BCFN) materials at the temperature range 550–650 °C is studied. The ionic conductivity separated by the electrode-blocking method exhibits a gradual increase at this temperature range. However, the electronic conductivity shows a steady curve. According to the characterization of thermogravimetry (TG) and O2-Temperature Programmed Desorption (O2-TPD), the desorption of oxygen and the formation of oxygen vacancies also occur at this temperature range. Using the oxygen vacancy diffusion coefficients Dchem (obtained by Electric Conductivity Relaxation (ECR)) and the oxygen vacancy content (obtained by TG), the theoretical ionic conductivity is calculated by Einstein–Nernst equation. The theoretical value is in good agreement with the experimental results, which means that the increase of BCFN ionic conductivity can be explained by the mostly ionized oxygen vacancies. The defect reaction of BCFN suggests that there's consumption of 4 + charge B sites ions accompanied with the formation of oxygen vacancies, which will stabilize the electrical conductivity according to the Zener double exchange effects. Besides, the X-ray photoelectron spectroscopic (XPS) results suggest that the B sites ions are also greatly influenced by the formation of oxygen vacancies. This may increase the exchange energy in the Zener double exchange effect and stabilize the electrical conductivity.