Improved Thermochemical Energy Storage Behavior of Manganese Oxide by Molybdenum Doping

Abstract

To improve the thermochemical energy storage (TCS) behavior of Mn2O3, several Mn–Mo oxides with varying amounts of MoO3 (0–30 wt%) were prepared by a precipitation method. The physico-chemical properties of the solids were studied by N2 adsorption–desorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), and H2-temperature-programmed reduction (TPR), while their TCS behavior was determined by thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). Apart from Mn2O3 and MoO3 phases, XRD revealed a mixed MnMoO4 phase for MoO3 loadings equal or higher than 1.5 wt%. All samples showed a well-formed coral-like surface morphology, particularly those solids with low MoO3 contents. This coral morphology was progressively decorated with compact and Mo-enriched MnMoO4 particles as the MoO3 content increased. TPR revealed that the redox behavior of Mn2O3 was significantly altered upon addition of Mo. The TCS behavior of Mn2O3 (mostly oxidation kinetics and redox cyclability) was enhanced by addition of low amounts of Mo (0.6 and 1.5% MoO3) without significantly increasing the reduction temperature of the solids. The coral morphology (which facilitated oxygen diffusion) and a smoother transition from the reduced to oxidized phase were suggested to be responsible for this improved TCS behavior. The samples containing 0.6 and 1.5 wt% of MoO3 showed outstanding cyclability after 45 consecutive reduction–oxidation cycles at high temperatures (600–1000 °C). These materials could potentially reach absorption efficiencies higher than 90% at concentration capacity values typical of concentrated solar power plants.

Keywords

• thermochemical energy storage
• Mn–Mo mixed oxides
• reducibility
• redox cyclability
• oxidation kinetics