Advancing oxygen separation: insights from experimental and computational analysis of La0.7Ca0.3Co0.3Fe0.6M0.1O3–δ (M = Cu, Zn) oxygen transport membranes
Guoxing Chen1(), Wenmei Liu2, Marc Widenmeyer3, Xiao Yu1, Zhijun Zhao4, Songhak Yoon1, Ruijuan Yan3, Wenjie Xie1,3, Armin Feldhoff4, Gert Homm1, Emanuel Ionescu1,3, Maria Fyta5,6(), Anke Weidenkaff1,3
1. Fraunhofer Research Institution for Materials Recycling and Resource Strategies IWKS, Alzenau 63755, Germany 2. Electrochemistry Laboratory, Paul Scherrer Institute, Villigen PSI 5232, Switzerland 3. Department of Materials and Earth Sciences, Materials and Resources, Technical University of Darmstadt, Darmstadt 64287, Germany 4. Institute of Physical Chemistry and Electrochemistry, Leibniz University Hannover, Hannover 30167, Germany 5. Institute for Computational Physics, University of Stuttgart, Stuttgart 70569, Germany 6. Computational Biotechnology, RWTH Aachen, Aachen 52074, Germany
In this study, perovskite-type La0.7Ca0.3Co0.3Fe0.6M0.1O3–δ (M = Cu, Zn) powders were synthesized using a scalable reverse co-precipitation method, presenting them as novel materials for oxygen transport membranes. The comprehensive study covered various aspects including oxygen permeability, crystal structure, conductivity, morphology, CO2 tolerance, and long-term regenerative durability with a focus on phase structure and composition. The membrane La0.7Ca0.3Co0.3Fe0.6Zn0.1O3–δ exhibited high oxygen permeation fluxes, reaching up to 0.88 and 0.64 mL·min−1·cm−2 under air/He and air/CO2 gradients at 1173 K, respectively. After 1600 h of CO2 exposure, the perovskite structure remained intact, showcasing superior CO2 resistance. A combination of first principles simulations and experimental measurements was employed to deepen the understanding of Cu/Zn substitution effects on the structure, oxygen vacancy formation, and transport behavior of the membranes. These findings underscore the potential of this highly CO2-tolerant membrane for applications in high-temperature oxygen separation. The enhanced insights into the oxygen transport mechanism contribute to the advancement of next-generation membrane materials.
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