Electrical Transport and Oxygen Exchange in the Superoxides of Potassium, 
Rubidium, and Cesium

Gerbig, O.; Merkle, R.; Maier, J.

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Electrical Transport and Oxygen Exchange in the Superoxides of Potassium, Rubidium, and Cesium

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Merkle, R.
Department Physical Chemistry of Solids (Joachim Maier), Max Planck Institute for Solid State Research, Max Planck Society;

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Maier, J.
Department Physical Chemistry of Solids (Joachim Maier), Max Planck Institute for Solid State Research, Max Planck Society;

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Citation

Gerbig, O., Merkle, R., & Maier, J. (2015). Electrical Transport and Oxygen Exchange in the Superoxides of Potassium, Rubidium, and Cesium. Advanced Functional Materials, 25(17), 2552-2563.

Cite as: https://hdl.handle.net/21.11116/0000-000E-CD26-1

Abstract

Conductivity, ionic transference number, and chemical diffusion coefficients are determined for KO2, RbO2, and CsO2. Based on such results, a defect-chemical model is constructed. These superoxides are found to exhibit a total conductivity in the range of 3 x 10(-7) to 5 x 10(-5) S cm(-1) at 200 degrees C with contributions from ionic and electronic carriers. The ionic conductivity is caused by alkali interstitials and superoxide vacancies as mobile defects, and is found to exceed the n-type electronic conductivity. O-18 isotope exchange on powder samples (monitoring the gas phase composition) shows that essentially all oxygen can be exchanged. At high pO(2) this largely occurs without breaking of the O-O bond-indicating a sufficient mobility of molecular superoxide species in the solid-and with an effective rate constant that is much higher than for other large-bandgap mixed conducting materials such as SrTiO3.