Chemical looping air separation (CLAS) is a promising technology for oxygen generation with high efficiency. The key challenge for CLAS is to design robust oxygen sorbents with suitable redox properties and fast redox kinetics. In this work, perovskite-structured Sr1-xCaxFe1-yCoyO3oxygen sorbents were investigated and demonstrated for oxygen production with tunable redox properties, high redox rate, and excellent thermal/steam stability. Cobalt doping at B site was found to be highly effective, 33% improvement in oxygen productivity was observed at 500 °C. Moreover, it stabilizes the perovskite structure and prevents phase segregation under pressure swing conditions in the presence of steam. Scalable synthesis of Sr0.8Ca0.2Fe0.4Co0.6O3oxygen sorbents was carried out through solid state reaction, co-precipitation, and sol-gel methods. Both co-precipitation and sol-gel methods are capable of producing Sr0.8Ca0.2Fe0.4Co0.6O3sorbents with satisfactory phase purity, high oxygen capacity, and fast redox kinetics. Large scale evaluation of Sr0.8Ca0.2Fe0.4Co0.6O3, using an automated CLAS testbed with over 300 g sorbent loading, further demonstrated the effectiveness of the oxygen sorbent to produce 95% pure O2with a satisfactory productivity of 0.04 gO2gsorbent−1h−1at 600 °C.
Oxygen coordination and vacancy ordering play an important role in dictating the functionality of complex oxides. In this work, an unconventional layering of oxygen ions in a mixed conductor SrCo1‐xFexO3‐δ(SCFO) thin film grown epitaxially on SrTiO3(STO) is reported. Scanning transmission electron microscopy (STEM) reveals alternating layers of oxygen deficiency along the growth direction, with the oxygen‐rich layer correlated with the neighboring Co,Fe‐site intensity, and contraction of the Sr–Sr distance. Density functional theory (DFT) calculations and STEM image simulations support the emergence of periodic (Co,Fe)O6and (Co,Fe)O4/(Co,Fe)O5layers, an ordering that is also sensitive to the Co:Fe ratio.
more » « less- Award ID(s):
- 2132623
- NSF-PAR ID:
- 10484557
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Interfaces
- Volume:
- 11
- Issue:
- 7
- ISSN:
- 2196-7350
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Perovskites are promising oxygen carriers for solar‐driven thermochemical fuel production due to higher oxygen exchange capacity. Despite their higher fuel yield capacity, La0.6Sr0.4MnO3perovskite materials present slow CO2‐splitting kinetics compared with state‐of‐the‐art CeO2. In order to improve the CO production rates, the incorporation of Cr in La0.6Sr0.4MnO3is explored based on thermodynamic calculations that suggest an enhanced driving force toward CO2splitting at high temperatures for La0.6Sr0.4Cr
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Abstract Solid–gas interactions at electrode surfaces determine the efficiency of solid‐oxide fuel cells and electrolyzers. Here, the correlation between surface–gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system La0.8Sr0.2Co0.2Fe0.8O3. The gas‐exchange kinetics are characterized by synthesizing epitaxial half‐cell geometries where three single‐variant surfaces are produced [i.e., La0.8Sr0.2Co0.2Fe0.8O3/La0.9Sr0.1Ga0.95Mg0.05O3−δ/SrRuO3/SrTiO3(001), (110), and (111)]. Electrochemical impedance spectroscopy and electrical conductivity relaxation measurements reveal a strong surface‐orientation dependency of the gas‐exchange kinetics, wherein (111)‐oriented surfaces exhibit an activity >3‐times higher as compared to (001)‐oriented surfaces. Oxygen partial pressure ()‐dependent electrochemical impedance spectroscopy studies reveal that while the three surfaces have different gas‐exchange kinetics, the reaction mechanisms and rate‐limiting steps are the same (i.e., charge‐transfer to the diatomic oxygen species). First‐principles calculations suggest that the formation energy of vacancies and adsorption at the various surfaces is different and influenced by the surface polarity. Finally, synchrotron‐based, ambient‐pressure X‐ray spectroscopies reveal distinct electronic changes and surface chemistry among the different surface orientations. Taken together, thin‐film epitaxy provides an efficient approach to control and understand the electrode reactivity ultimately demonstrating that the (111)‐surface exhibits a high density of active surface sites which leads to higher activity.
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