Oxygen surface exchange kinetics and stability of (La,Sr)2 CoO4±δ/La 1-xSrxMO3-δ (M = Co and Fe) hetero-interfaces at intermediate temperatures

Lee, Dongkyu; Lee, Yueh-Lin; Hong, Wesley T.; Biegalski, Michael D.; Morgan, Dane; Shao-Horn, Yang

doi:10.1039/C4TA05795C

Title: Oxygen surface exchange kinetics and stability of (La,Sr)₂ CoO_4±δ/La _1-xSr_xMO_3-δ (M = Co and Fe) hetero-interfaces at intermediate temperatures

Journal Article · Thu Nov 13 00:00:00 EST 2014 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/C4TA05795C· OSTI ID:1185681

Lee, Dongkyu ^[1]; Lee, Yueh-Lin ^[1]; Hong, Wesley T. ^[2]; Biegalski, Michael D. ^[3]; Morgan, Dane ^[4]; Shao-Horn, Yang ^[5]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Electrochemical Energy Lab. and Dept. of Mechanical Engineering
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Electrochemical Energy Lab. and Dept. of Materials Science and Engineering
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Electrochemical Energy Lab., Dept. of Mechanical Engineering, and Dept. of Materials Science and Engineering

Heterostructured oxide interfaces created by decorating Ruddlesden-Popper phases (A2BO4) or perovskites on perovskites have shown not only pronounced cation segregation at the interface and in the A2BO4 structure but also much enhanced kinetics for oxygen electrocatalysis at elevated temperatures. In this study, we report and compare the time-dependent surface exchange kinetics and stability of (La_0.5Sr_0.5)₂CoO₄ -decorated (LSC₂₁₄) La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF₁₁₃) and La_0.8Sr_0.2CoO_3-δ (LSC₁₁₃) thin films. While LSC₂₁₄ decoration on LSC₁₁₃greatly reduced the degradation in the surface exchange kinetics as a function of time relative to LSC₁₁₃, LSCF₁₁₃ with LSC₂₁₄ coverage showed comparable surface exchange kinetics and stability to LSCF₁₁₃. This difference can be explained by greater surface stability of LSCF₁₁₃ than LSC₁₁₃ under testing conditions, and that LSC₂₁₄ decoration on LSC₁₁₃ reduced the decomposition of LSC₁₁₃ to form secondary phases that impedes oxygen exchange kinetics, and thus resulted in enhanced stability. This hypothesis is supported by the observations that annealing at 550 °C led to the formation of Sr-rich secondary particles on LSC₁₁₃ while no such particles were observed on LSCF₁₁₃. Density functional theory (DFT) computation provides further support, which revealed greater capacity of surface Sr segregation for LSCF₁₁₃ having SrO termination than LSC₁₁₃ having (La_0.25Sr_0.75)O termination for the experimental conditions, and lower energy gain to move Sr from LSCF₁₁₃ into LSC₂₁₄ relative to the LSC₂₁₄-LSC₁₁₃ system.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1185681

Journal Information:: Journal of Materials Chemistry. A, Vol. 3, Issue 5; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 53 works

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Sm _0.5Sr_0.5CoO_3-δ Surface Modification of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ-Ce_0.9Gd0.1_2-δ Composite Oxygen Electrodes for Solid Oxide Electrochemical Cells

Journal Article · Wed Nov 25 00:00:00 EST 2020 · Journal of the Electrochemical Society · OSTI ID:1185681

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Electrochemically influenced cation inter-diffusion and Co₃O₄ formation on La_0.6Sr_0.4CoO₃ infiltrated into SOFC cathodes

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Title: Oxygen surface exchange kinetics and stability of (La,Sr)2 CoO4±δ/La 1-xSrxMO3-δ (M = Co and Fe) hetero-interfaces at intermediate temperatures

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Title: Oxygen surface exchange kinetics and stability of (La,Sr)₂ CoO_4±δ/La _1-xSr_xMO_3-δ (M = Co and Fe) hetero-interfaces at intermediate temperatures