Multiscale modeling and experimental interpretation of perovskite oxide materials in thermochemical energy storage and conversion for application in concentrating solar power

Abstract

Decarbonization of the electric grid is fundamentally limited by the intermittency of renewable resources such as wind and solar. Therefore, energy storage will play a significant role in the future of grid-scale energy generation to overcome the intermittency issues. For this reason, concentrating solar power (CSP) plants have been a renewable energy generation technology of interest due to their ability to participate in cost effective and efficient thermal energy storage. However, the ability to dynamically dispatch a CSP plant to meet energy demands is currently limited by the large quantities of sensible thermal energy storage material needed in a molten salt plant. Perovskite oxides have been suggested as a thermochemical energy storage material to enhance the energy storage capabilities of particle-based CSP plants, which combine sensible and chemical modes of energy storage. In this dissertation, computational models are used to establish the thermochemical energy storage potential of select perovskite compositions, identify system configurations that promote high values of energy storage and solar-to-electric efficiency, assess the kinetic and transport limitation of the chemical mode of energy storage, and create receiver and reoxidation reactor models capable of aiding in component design. A methodology for determining perovskite thermochemical energy storage potential is developed based on point defect models to represent perovskite non-stoichiometry as a function of temperature and gas phase oxygen partial pressure. The thermodynamic parameters necessary for the model are extracted from non-stoichiometry measurements by fitting the model using an optimization routine. The procedure is demonstrated for Ca0.9Sr0.1MnO3-d which displayed combined energy storage values of 705.7 kJ/kg by cycling between 773 K and 0.21 bar oxygen to 1173 K and 10-4 bar oxygen. Abstract Thermodynamic system-level models capable of exploiting perovskite redox chemistry for energy storage in CSP plants are presented. Comparisons of sweep gas and vacuum pumping reduction as well as hot storage conditions indicate that solar-to-electric efficiencies are higher for sweep gas reduction system at equivalent values of energy storage if the energy parasitics of commercially available devices are considered. However, if vacuum pump efficiency between 15% and 30% can be achieved, the reduction methods will be approximately equal. Reducing condition oxygen partial pressures below 10-3 bar for sweep gas reduction and 10-2 bar for vacuum pumping reduction result in large electrical parasitics, which significantly reduce solar-to-electric efficiency. A model based interpretation of experimental measurements made for perovskite redox cycling using sweep gas in a packed bed is presented. The model indicates that long reduction times for equilibrating perovskites with low oxygen partial pressure sweep gas, compared to reoxidation, are primarily due to the oxygen carrying capacity of high purity sweep gas and not surface kinetic limitations. Therefore, achieving rapid reduction in the limited receiver residence time will be controlled by the quantity of sweep gas introduced. Effective kinetic parameters considering surface reaction and radial particle diffusion are fit to the experimental data. Variable order rate expressions without significant particle radial diffusion limitations are shown to be capable of representing the reduction and oxidation data. Modeling of a particle reduction receiver using continuous flow of perovskite solid and sweep gas in counter-flow configuration has identified issues with managing the oxygen evolved by the solid as well as sweep gas flow rates. Introducing sweep gas quantities necessary for equilibrating the solid with oxygen partial pressures below 10-2 are shown to result in gas phase velocities above the entrainment velocity of 500 um particles. Receiver designs with considerations for gas management are investigated and the results indicate that degrees of reduction corresponding to only oxygen partial pressures of 10-2 bar are attained. Numerical investigation into perovskite thermochemical energy storage indicates that achieving high levels of reduction through sweep gas or vacuum pumping to lower gas phase oxygen partial pressure below 10-2 bar display issues with parasitic energy consumption and gas phase management. Therefore, focus on material development should place a premium on thermal reduction and reduction by shifting oxygen partial pressure between ambient and 10-2 bar. Such a material would enable the development of a system with high solar-to-electric efficiencies and degrees of reduction which are attainable in realistic component geometries.