Impact of the Sr content on the redox thermodynamics and kinetics of Ca1−xSrxMnO3−δ for tailored properties

Abstract

CaMnO_3−δ-based perovskites find application in a variety of thermochemical cycles, e.g. oxygen partial pressure adjustment, chemical looping processes, and thermochemical energy storage. The applicability of these materials is governed by their thermodynamic and kinetic properties. Therefore, tunability of these properties is desirable to adapt the material to the required conditions. In this study, the effect of Sr content in Ca_1−xSr_xMnO_3−δ on thermodynamics and kinetics is investigated by thermogravimetric analysis. The thermodynamics are measured in the temperature range of 873 K to 1473 K with oxygen partial pressures of 1 × 10⁻⁴ bar to 0.8 bar. The oxidation kinetics were characterized in the temperature range from 473 K to 673 K with oxygen partial pressures of 0.01 bar to 1 bar. The reduction kinetics were very rapid in the temperature range of 873 K to 1023 K, with the measured rates limited by the constraints of the measurement device. The results show that with increasing Sr content the structural changes of the material decrease the reduction enthalpy and the oxidation activation energy. This not only leads to a tunability of material properties, but can also be used to predict changes of these properties when only the structural changes are known.