Comparing the solar-to-fuel energy conversion efficiency of ceria and perovskite based thermochemical redox cycles for splitting H2O and CO2

A thermodynamic analysis was conducted on a solar thermochemical plant for syngas generation via H2O/CO2-splitting redox cycles in order to determine the performance of six candidate redox materials under an array of operation conditions. The values obtained for the solar-to-fuel energy conversion efficiency are higher in relative order Zr-doped CeO2 > undoped CeO2 > La0.6Ca0.4MnO3 > La0.6Ca0.4Mn0.6Al0.4O3 > La0.6Sr0.4MnO3 > La0.6Sr0.4Mn0.6Al0.4O3. This ordering is attributed to their relative reducibility and reoxidizability, where the doped and undoped ceria, that favor oxidation, outperform perovskites, that favor reduction and therefore require high flowrates of excess H2O and CO2 during re-oxidation. Solids-solid heat recuperation during the temperature swing between the redox steps is crucial, particularly for ceria because of its low specific oxygen exchange capacity per mole and cycle. Conversely, the efficiencies of the perovskites are more dependent on gas-gas heat recuperation due to the massive excess of H2O/CO2. Redox material thermodynamics and plant/reactor performance are closely coupled, and must be considered together to maximize efficiency. Overall, we find that Zr-CeO2 is the most promising redox material, while perovskites which seem promising due to high H-2/CO production capacities under large H2O/CO2 flow rates, perform poorly from an efficiency perspective due to the high heating duties, especially for steam. (C) 2018 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.