(174e) Examining the Solar-to-Fuel Efficiency of Ceria and Perovskite Thermochemical Redox Cycles for Splitting H2O and CO2
Ceria and perovskite based materials have attracted significant attention for use in solar thermochemical H2O and CO2 splitting cycles. Ceria based materials, the current gold standard, tend to favor the oxidation reaction while perovskite materials tend to favored the reduction reaction. To date, most materials comparisons have focused on fuel production capacity per cycle and have neglected the effects of the plant and reactions on the overall solar to fuel conversion efficiency. Therefore, a thermodynamic model of a solar thermochemical gas (CO2/H2O) splitting plant was constructed and used to evaluate the performance of six candidate redox materials (two ceria and four perovskite 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 re-oxidizability, 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 H2/CO production capacities under large H2O/CO2 flow rates, perform poorly from an efficiency perspective due to the high heating duties, especially for steam.