Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes

Cortney R. Kreller; T. J. McDonald; Stuart B. Adler; Ethan J. Crumlin; Eva Mutoro; Sung Jin Ahn; G. J. la O'; Yang Shao-Horn; Michael D. Biegalski; Hans M. Christen; Richard R. Chater; John A. Kilner

doi:10.1149/2.021309jes

Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes

Cortney R. Kreller, T. J. McDonald, Stuart B. Adler, Ethan J. Crumlin, Eva Mutoro, Sung Jin Ahn, G. J. la O', Yang Shao-Horn, Michael D. Biegalski, Hans M. Christen, Richard R. Chater, John A. Kilner

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26 Scopus citations

Abstract

Films of La0.8Sr0.2CoO3-δ (LSC-82) with 45 and 90 nm thickness were grown epitaxially on (001) oriented single crystal yttriastabilized zirconia with a thin gadolinium-doped ceria interlayer using pulsed laser deposition, and characterized using X-ray diffraction (XRD), depth-profile secondary mass spectrometry (DP-SIMS), and linear and nonlinear electrochemical impedance spectroscopy (EIS and NLEIS). The films were found to exhibit in-plane tensile strain and normal compressive strain (with overall increased lattice volume) relative to freestanding cubic LSC-82. The films also possess a compositional La/Sr gradient across their thickness, with enhanced Sr2+ composition (within the perovskite lattice) at the gas-exposed surface. The oxygen storage capacity of the films at 450-600°C (as measured using EIS capacitance) is greatly enhanced relative to freestanding cubic LSC-82, consistent with an apparent increase in oxygen-vacancy concentration at the gas-exposed surface of the films (as revealed by NLEIS). These results can be explained by a two-layer model in which a finite thickness of the perovskite lattice near the surface has an enhanced Sr dopant concentration, leading to a much higher concentration of oxygen vacancies than the underlying bulk material of nominal Sr composition. The nonlinear electrochemical response of the film is consistent with a dissociative adsorption rate law, provided the enhanced bulk vacancy concentration near the surface is included in the analysis. © 2013 The Electrochemical Society. All rights reserved.

Original language	English (US)
Pages (from-to)	F931-F942
Number of pages	1
Journal	JOURNAL OF THE ELECTROCHEMICAL SOCIETY
Volume	160
Issue number	9
DOIs	https://doi.org/10.1149/2.021309jes
State	Published - 2013
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2021-09-21
Acknowledgements: This work was supported in part by National Science Foundation Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET) under award numbers 0829171 and 0844526, the U.S. Department of Energy (SISGR DE-SC0002633) and King Abdullah University of Science and Technology. Work at ORNL (including contributions by MDB and HMC) was supported by the U.S. Department of Energy, Basic Energy Sciences, Scientific User Facilities Division.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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10.1149/2.021309jes

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Kreller, C. R., McDonald, T. J., Adler, S. B., Crumlin, E. J., Mutoro, E., Ahn, S. J., la O', G. J., Shao-Horn, Y., Biegalski, M. D., Christen, H. M., Chater, R. R., & Kilner, J. A. (2013). Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 160(9), F931-F942. https://doi.org/10.1149/2.021309jes

@article{0f433f7af6d44ddfa0cffb632c65a504,

title = "Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes",

abstract = "Films of La0.8Sr0.2CoO3-δ (LSC-82) with 45 and 90 nm thickness were grown epitaxially on (001) oriented single crystal yttriastabilized zirconia with a thin gadolinium-doped ceria interlayer using pulsed laser deposition, and characterized using X-ray diffraction (XRD), depth-profile secondary mass spectrometry (DP-SIMS), and linear and nonlinear electrochemical impedance spectroscopy (EIS and NLEIS). The films were found to exhibit in-plane tensile strain and normal compressive strain (with overall increased lattice volume) relative to freestanding cubic LSC-82. The films also possess a compositional La/Sr gradient across their thickness, with enhanced Sr2+ composition (within the perovskite lattice) at the gas-exposed surface. The oxygen storage capacity of the films at 450-600°C (as measured using EIS capacitance) is greatly enhanced relative to freestanding cubic LSC-82, consistent with an apparent increase in oxygen-vacancy concentration at the gas-exposed surface of the films (as revealed by NLEIS). These results can be explained by a two-layer model in which a finite thickness of the perovskite lattice near the surface has an enhanced Sr dopant concentration, leading to a much higher concentration of oxygen vacancies than the underlying bulk material of nominal Sr composition. The nonlinear electrochemical response of the film is consistent with a dissociative adsorption rate law, provided the enhanced bulk vacancy concentration near the surface is included in the analysis. {\textcopyright} 2013 The Electrochemical Society. All rights reserved.",

author = "Kreller, {Cortney R.} and McDonald, {T. J.} and Adler, {Stuart B.} and Crumlin, {Ethan J.} and Eva Mutoro and Ahn, {Sung Jin} and {la O'}, {G. J.} and Yang Shao-Horn and Biegalski, {Michael D.} and Christen, {Hans M.} and Chater, {Richard R.} and Kilner, {John A.}",

note = "KAUST Repository Item: Exported on 2021-09-21 Acknowledgements: This work was supported in part by National Science Foundation Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET) under award numbers 0829171 and 0844526, the U.S. Department of Energy (SISGR DE-SC0002633) and King Abdullah University of Science and Technology. Work at ORNL (including contributions by MDB and HMC) was supported by the U.S. Department of Energy, Basic Energy Sciences, Scientific User Facilities Division. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2013",

doi = "10.1149/2.021309jes",

language = "English (US)",

volume = "160",

pages = "F931--F942",

journal = "JOURNAL OF THE ELECTROCHEMICAL SOCIETY",

issn = "1945-7111",

publisher = "Electrochemical Society",

number = "9",

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TY - JOUR

T1 - Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes

AU - Kreller, Cortney R.

AU - McDonald, T. J.

AU - Adler, Stuart B.

AU - Crumlin, Ethan J.

AU - Mutoro, Eva

AU - Ahn, Sung Jin

AU - la O', G. J.

AU - Shao-Horn, Yang

AU - Biegalski, Michael D.

AU - Christen, Hans M.

AU - Chater, Richard R.

AU - Kilner, John A.

N1 - KAUST Repository Item: Exported on 2021-09-21 Acknowledgements: This work was supported in part by National Science Foundation Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET) under award numbers 0829171 and 0844526, the U.S. Department of Energy (SISGR DE-SC0002633) and King Abdullah University of Science and Technology. Work at ORNL (including contributions by MDB and HMC) was supported by the U.S. Department of Energy, Basic Energy Sciences, Scientific User Facilities Division. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2013

Y1 - 2013

N2 - Films of La0.8Sr0.2CoO3-δ (LSC-82) with 45 and 90 nm thickness were grown epitaxially on (001) oriented single crystal yttriastabilized zirconia with a thin gadolinium-doped ceria interlayer using pulsed laser deposition, and characterized using X-ray diffraction (XRD), depth-profile secondary mass spectrometry (DP-SIMS), and linear and nonlinear electrochemical impedance spectroscopy (EIS and NLEIS). The films were found to exhibit in-plane tensile strain and normal compressive strain (with overall increased lattice volume) relative to freestanding cubic LSC-82. The films also possess a compositional La/Sr gradient across their thickness, with enhanced Sr2+ composition (within the perovskite lattice) at the gas-exposed surface. The oxygen storage capacity of the films at 450-600°C (as measured using EIS capacitance) is greatly enhanced relative to freestanding cubic LSC-82, consistent with an apparent increase in oxygen-vacancy concentration at the gas-exposed surface of the films (as revealed by NLEIS). These results can be explained by a two-layer model in which a finite thickness of the perovskite lattice near the surface has an enhanced Sr dopant concentration, leading to a much higher concentration of oxygen vacancies than the underlying bulk material of nominal Sr composition. The nonlinear electrochemical response of the film is consistent with a dissociative adsorption rate law, provided the enhanced bulk vacancy concentration near the surface is included in the analysis. © 2013 The Electrochemical Society. All rights reserved.

AB - Films of La0.8Sr0.2CoO3-δ (LSC-82) with 45 and 90 nm thickness were grown epitaxially on (001) oriented single crystal yttriastabilized zirconia with a thin gadolinium-doped ceria interlayer using pulsed laser deposition, and characterized using X-ray diffraction (XRD), depth-profile secondary mass spectrometry (DP-SIMS), and linear and nonlinear electrochemical impedance spectroscopy (EIS and NLEIS). The films were found to exhibit in-plane tensile strain and normal compressive strain (with overall increased lattice volume) relative to freestanding cubic LSC-82. The films also possess a compositional La/Sr gradient across their thickness, with enhanced Sr2+ composition (within the perovskite lattice) at the gas-exposed surface. The oxygen storage capacity of the films at 450-600°C (as measured using EIS capacitance) is greatly enhanced relative to freestanding cubic LSC-82, consistent with an apparent increase in oxygen-vacancy concentration at the gas-exposed surface of the films (as revealed by NLEIS). These results can be explained by a two-layer model in which a finite thickness of the perovskite lattice near the surface has an enhanced Sr dopant concentration, leading to a much higher concentration of oxygen vacancies than the underlying bulk material of nominal Sr composition. The nonlinear electrochemical response of the film is consistent with a dissociative adsorption rate law, provided the enhanced bulk vacancy concentration near the surface is included in the analysis. © 2013 The Electrochemical Society. All rights reserved.

UR - http://hdl.handle.net/10754/671328

UR - https://iopscience.iop.org/article/10.1149/2.021309jes

UR - http://www.scopus.com/inward/record.url?scp=84881533204&partnerID=8YFLogxK

U2 - 10.1149/2.021309jes

DO - 10.1149/2.021309jes

M3 - Article

SN - 1945-7111

VL - 160

SP - F931-F942

JO - JOURNAL OF THE ELECTROCHEMICAL SOCIETY

JF - JOURNAL OF THE ELECTROCHEMICAL SOCIETY

IS - 9

ER -

Origin of Enhanced Chemical Capacitance in La0.8Sr0.2CoO3-delta Thin Film Electrodes

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