Advancing oxygen separation: insights from experimental and computational analysis of La_0.7Ca_0.3Co_0.3Fe_0.6M_0.1O_3–δ (M = Cu, Zn) oxygen transport membranes

Abstract

In this study, perovskite-type La_0.7Ca_0.3Co_0.3Fe_0.6M_0.1O_3–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 La_0.7Ca_0.3Co_0.3Fe_0.6Zn_0.1O_3–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.

Key words： perovskite; oxygen permeation; membrane; oxygen ions diffusion; oxygen vacancy; formation energy; energy barrier

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

G.C., M.W., and A.W. kindly thank the Federal Ministry of Education and Research for financial support during PiCK project (Grant No. 03SFK2S3B). G.C., G.H., and A.W. kindly thank the Hydrogen performance center in Hesse for financial support during the Green materials for Green H₂ project. M.W. and A.W. kindly thank the Federal Ministry of Education and Research for financial support during the NexPlas project (Grant No. 03SF0618B). The simulations presented in this work were performed on the computational resource For HLR II funded by the Ministry of Science, Research and the Arts Baden-Württemberg and the Deutsche Forschungsgemeinschaft. W.L. and M.F. are thankful for being granted access to these facilities.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2421-5 and is accessible for authorized users.

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