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In complex perovskite-type oxides, which have been studied as cathode materials, the thermal expansion coefficient (TEC) increases with the increase in the oxygen ionic conductivity. The aim of the present study is to explain such a behavior from a chemical bond point of view. For the perovskite oxides expressed as A 1-x A x B 1-y B y O 3-δ and ABO 3 , the ionicity of A O and B O bonds and the thermal expansion coefficient were evaluated theoretically by using semiempirical methods. It is found that the thermal expansion coefficient and the oxygen ionic conductivity decrease with the increase in the difference of the ionicity between A O and B O bonds.

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In complex perovskite oxides, it has been reported that the thermal expansion coefficient increases with the increase in the oxygen ionic conductivity. However, its theoretical background has not been clarified yet. In the present study, a model to understand the relationship is presented. By analyzing the experimental data using the theoretical expression derived, microscopic quantities related to ionic transport has been obtained.

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