Oxygen Crossover in Solid–Solid Heat Exchangers for Solar Water and Carbon Dioxide Splitting: A Thermodynamic Analysis

In solar thermochemical redox cycles for H2O/CO2-splitting, a large portion of the overall energy demand of the system is associated with heating the redox material from the oxidation temperature to the reduction temperature. Hence, an important measure to improve the efficiency is recuperation of sensible heat stored in the redox material. A solid–solid heat exchanger can be subjected to undesirable oxygen crossover, which decreases the oxygen uptake capacity of the redox material and consequently the system efficiency. We investigate the extent of this crossover in ceria-based cycles, to identify, under which conditions a heat exchanger that allows oxygen crossover can improve the system efficiency. In a thermodynamic analysis, we calculate the amount of transferred oxygen as a function of the heat exchanger efficiency and show the system efficiency of such a concept. A second law analysis is applied to the model to check the feasibility of calculated points of operation. For the investigated parameter set, the heat exchanger design improves the system efficiency by a factor of up to 2.1.

Oxygen Crossover in Solid-Solid Heat Exchangers for Solar Water and Carbon Dioxide Splitting: A Thermodynamic Analysis

In solar thermochemical redox cycles for H2O/CO2-splitting, a large portion of the overall energy demand of the system is associated with heating the redox material from the oxidation temperature to the reduction temperature. Hence, an important measure to improve the efficiency is recuperation of sensible heat stored in the redox material. A solid-solid heat exchanger can be subject to undesirable oxygen crossover, which decreases the oxygen uptake capacity of the redox material and consequently the system efficiency. We investigate the extent of this crossover in ceria based cycles, to identify, under which conditions a heat exchanger that allows oxygen crossover can improve the system efficiency. In a thermodynamic analysis we calculate the amount of transferred oxygen as a function of the heat exchanger efficiency and show the system efficiency of such a concept. A second law analysis is applied to the model to check the feasibility of calculated points of operation. For the investigated parameter set the heat exchanger design improves the system efficiency by a factor of up to 2.1.

Redox Oxides-Based Solar Thermochemistry and Its Materialization to Reactor/Heat Exchanger Concepts for Efficient Solar Energy Harvesting, Transformation and Storage

Ca-Mn-based perovskites doped in their A- and B-site were synthesized and comparatively tested versus the Co3O4/CoO and (Mn,Fe)2O3/(Mn,Fe)3O4 redox pairs with respect to thermochemical storage and oxygen pumping capability, as a function of the kind and extent of dopant. The perovskites' induced heat effects measured via differential scanning calorimetry are substantially lower: the highest reaction enthalpy recorded by the CaMnO3–δ composition was only 14.84 kJ/kg compared to 461.1 kJ/kg for Co3O4/CoO and 161.0 kJ/kg for (Mn,Fe)2O3/(Mn,Fe)3O4. Doping of Ca with increasing content of Sr decreased these heat effects; more than 20 at % Sr eventually eliminated them. Perovskites with Sr instead of Ca in the A-site exhibited also negligible heat effects, irrespective of the kind of B site cation. On the contrary, perovskite compositions characterized by high oxygen release/uptake can operate as thermochemical oxygen pumps enhancing the performance of water/carbon dioxide splitting materials. Oxygen pumping via Ca0.9Sr0.1MnO3–δ and SrFeO3–δ doubled and tripled, respectively, the total oxygen absorbed by ceria during its re-oxidation versus that absorbed without their presence. Such effective pumping compositions exhibited practically no shrinkage during one heat-up/cool-down cycle. However, they demonstrated an increase of the coefficient of linear expansion due to the superposition of “chemical expansion” to thermal-only one, the effect of which on the long-term dimensional stability has to be further quantified through extended cyclic operation.

Thermodynamic Analyses of Fuel Production Via Solar-Driven Ceria-Based Nonstoichiometric Redox Cycling: A Case Study of the Isothermal Membrane Reactor System

A thermodynamic model of an isothermal ceria-based membrane reactor system is developed for fuel production via solar-driven simultaneous reduction and oxidation reactions. Inert sweep gas is applied on the reduction side of the membrane. The model is based on conservation of mass, species, and energy along with the Gibbs criterion. The maximum thermodynamic solar-to-fuel efficiencies are determined by simultaneous multivariable optimization of operational parameters. The effects of gas heat recovery and reactor flow configurations are investigated. The results show that maximum efficiencies of 1.3% (3.2%) and 0.73% (2.0%) are attainable for water splitting (carbon dioxide splitting) under counter- and parallel-flow configurations, respectively, at an operating temperature of 1900 K and 95% gas heat recovery effectiveness. In addition, insights on potential efficiency improvement for the membrane reactor system are further suggested. The efficiencies reported are found to be much lower than those reported in literature. We demonstrate that the thermodynamic models reported elsewhere can violate the Gibbs criterion and, as a result, lead to unrealistically high efficiencies. The present work offers enhanced understanding of the counter-flow membrane reactor and provides more accurate upper efficiency limits for membrane reactor systems.