The electrical conductivities of Sr
2CoRO
6 (R=Mo, Nb) under different oxygen partial pressures and their crystal structures were investigated. Their conducting mechanisms were proposed. X-ray photoelectron spectra revealed that the dominated oxidation state of Co
2+ was in Sr
2CoMoO
6 but Co
3+ in Sr
2CoNbO
6. The crystal lattice structures of Sr
2CoRO
6 were identified by X-ray diffraction and their parameters were calculated by using Rietveld method. The refined crystal structures of Sr
2CoRO
6 have been used to construct their own conducting channel model. And the electrical conductivities were measured by using an electrochemical workstation with four-terminals method through controlling the oxygen partial pressure of the testing environment. The results show that the electrical conductivity of Sr
2CoMoO
6 is 0.36 S·cm
−1, much lower than that of Sr
2CoNbO
6 (7.81 S·cm
−1) in air at 973 K, which is assigned to the difference of their conducting channels. And the electrical conductivity of Sr
2CoMoO
6 increased linearly with the decrease in
PO2, reaching 2.05 S·cm
−1 when
PO2 = 10
−21 atm at 973 K, while Sr
2CoNbO
6 presented an opposite trend. It was supposed that the different valences of cobalt in Sr
2CoMoO
6 and Sr
2CoNbO
6 lead to the different electron conducting channels and different changing trends of electrical conductivities with the decrease in oxygen partial pressure.
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