Fast Redox Kinetics in SrCo1-xSbxO3- δ Perovskites for Thermochemical Energy Storage

George E. Wilson; Ieuan D. Seymour; Andrea Cavallaro; Stephen J. Skinner; Ainara Aguadero

doi:10.1149/1945-7111/ac62c5

Fast Redox Kinetics in SrCo_1-xSb_xO_{3- δ}Perovskites for Thermochemical Energy Storage

George E. Wilson, Ieuan D. Seymour, Andrea Cavallaro, Stephen J. Skinner^*, Ainara Aguadero

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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Abstract

The use of perovskite materials for thermochemical energy storage and oxygen separation has been gaining momentum in recent years due to their ability to topotactically exchange large volumes of oxygen, and their chemical and structural flexibility. B-site substituted SrCoO3-δ derivatives have previously been investigated as promising materials for intermediate temperature solid oxide fuel cell cathodes due to the stabilization of a 3 C perovskite structure with high electronic and ionic conductivity that allows large oxygen storage capabilities. Here, antimony-substituted strontium cobalt oxides are investigated and identified as new candidate materials for thermochemical oxygen separation applications. In this work we shed light on the exceptional redox kinetics and cyclability of antimony-substituted variants undergoing oxygen exchange at intermediate temperatures (500 to 800 C). Through the use of density functional theory and isothermal gas atmosphere switching, we demonstrate how the inductive effect of the more electronegative antimony dopants in the Co position, facilitates the kinetics of metal oxide oxidation, whilst hindering reduction reactions. SrCo0.95Sb0.05O3-δ was identified to isothermally evolve 3.76 cm3 g-1 of oxygen at 500 C and calculated to produce up to 10.44 cm3 g-1 under temperature-swing reaction configurations aligning with previously reported materials.

Original language	English
Article number	044509
Number of pages	9
Journal	Journal of the Electrochemical Society
Volume	169
Issue number	4
Early online date	8 Apr 2022
DOIs	https://doi.org/10.1149/1945-7111/ac62c5
Publication status	Published - Apr 2022

Bibliographical note

Acknowledgments
The authors would like to acknowledge Mr Richard Sweeney from the Imperial College London Materials department's XRD and Thermal Analysis suite and wish him a happy and well-deserved retirement. Further acknowledgements are to the Harvey Flowers Electron Microscopy suite at Imperial College London, the Imperial College Research Computing Service (10.14469/hpc/2232), and other associated support services used during this work.

Funding
Funding for this work was provided by EPSRC CDT in Fuel Cells and their fuels: EP/L015749/1. SJS, AA and IDS thank the EPSRC for funding through a Platform funding award (EP/R002010/1).

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Cite this

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title = "Fast Redox Kinetics in SrCo1-xSbxO3- δ Perovskites for Thermochemical Energy Storage",

abstract = "The use of perovskite materials for thermochemical energy storage and oxygen separation has been gaining momentum in recent years due to their ability to topotactically exchange large volumes of oxygen, and their chemical and structural flexibility. B-site substituted SrCoO3-δ derivatives have previously been investigated as promising materials for intermediate temperature solid oxide fuel cell cathodes due to the stabilization of a 3 C perovskite structure with high electronic and ionic conductivity that allows large oxygen storage capabilities. Here, antimony-substituted strontium cobalt oxides are investigated and identified as new candidate materials for thermochemical oxygen separation applications. In this work we shed light on the exceptional redox kinetics and cyclability of antimony-substituted variants undergoing oxygen exchange at intermediate temperatures (500 to 800 C). Through the use of density functional theory and isothermal gas atmosphere switching, we demonstrate how the inductive effect of the more electronegative antimony dopants in the Co position, facilitates the kinetics of metal oxide oxidation, whilst hindering reduction reactions. SrCo0.95Sb0.05O3-δ was identified to isothermally evolve 3.76 cm3 g-1 of oxygen at 500 C and calculated to produce up to 10.44 cm3 g-1 under temperature-swing reaction configurations aligning with previously reported materials.",

author = "Wilson, {George E.} and Seymour, {Ieuan D.} and Andrea Cavallaro and Skinner, {Stephen J.} and Ainara Aguadero",

note = "Acknowledgments The authors would like to acknowledge Mr Richard Sweeney from the Imperial College London Materials department's XRD and Thermal Analysis suite and wish him a happy and well-deserved retirement. Further acknowledgements are to the Harvey Flowers Electron Microscopy suite at Imperial College London, the Imperial College Research Computing Service (10.14469/hpc/2232), and other associated support services used during this work. Funding Funding for this work was provided by EPSRC CDT in Fuel Cells and their fuels: EP/L015749/1. SJS, AA and IDS thank the EPSRC for funding through a Platform funding award (EP/R002010/1). ",

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N2 - The use of perovskite materials for thermochemical energy storage and oxygen separation has been gaining momentum in recent years due to their ability to topotactically exchange large volumes of oxygen, and their chemical and structural flexibility. B-site substituted SrCoO3-δ derivatives have previously been investigated as promising materials for intermediate temperature solid oxide fuel cell cathodes due to the stabilization of a 3 C perovskite structure with high electronic and ionic conductivity that allows large oxygen storage capabilities. Here, antimony-substituted strontium cobalt oxides are investigated and identified as new candidate materials for thermochemical oxygen separation applications. In this work we shed light on the exceptional redox kinetics and cyclability of antimony-substituted variants undergoing oxygen exchange at intermediate temperatures (500 to 800 C). Through the use of density functional theory and isothermal gas atmosphere switching, we demonstrate how the inductive effect of the more electronegative antimony dopants in the Co position, facilitates the kinetics of metal oxide oxidation, whilst hindering reduction reactions. SrCo0.95Sb0.05O3-δ was identified to isothermally evolve 3.76 cm3 g-1 of oxygen at 500 C and calculated to produce up to 10.44 cm3 g-1 under temperature-swing reaction configurations aligning with previously reported materials.

AB - The use of perovskite materials for thermochemical energy storage and oxygen separation has been gaining momentum in recent years due to their ability to topotactically exchange large volumes of oxygen, and their chemical and structural flexibility. B-site substituted SrCoO3-δ derivatives have previously been investigated as promising materials for intermediate temperature solid oxide fuel cell cathodes due to the stabilization of a 3 C perovskite structure with high electronic and ionic conductivity that allows large oxygen storage capabilities. Here, antimony-substituted strontium cobalt oxides are investigated and identified as new candidate materials for thermochemical oxygen separation applications. In this work we shed light on the exceptional redox kinetics and cyclability of antimony-substituted variants undergoing oxygen exchange at intermediate temperatures (500 to 800 C). Through the use of density functional theory and isothermal gas atmosphere switching, we demonstrate how the inductive effect of the more electronegative antimony dopants in the Co position, facilitates the kinetics of metal oxide oxidation, whilst hindering reduction reactions. SrCo0.95Sb0.05O3-δ was identified to isothermally evolve 3.76 cm3 g-1 of oxygen at 500 C and calculated to produce up to 10.44 cm3 g-1 under temperature-swing reaction configurations aligning with previously reported materials.

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