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Title: Temporal and thermal evolutions of surface Sr-segregation in pristine and atomic layer deposition modified La0.6Sr0.4CoO3-δ epitaxial films

Abstract

The bulk-to-surface Sr segregation can seriously compromise the stability of oxygen electrocatalysis in La1-xSrxCoO3-δ and limit its practical applications such as in solid oxide fuel cells. In this work, we show via in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) that the surface Sr-segregation is a kinetically fast process and the equilibrium surface Sr-concentration follows Arrhenius law from 250 to 520 °C at a fixed pO2 = 1 × 10-3 atm. Furthermore, we also show that application of a nanoscaled, atomic layer deposition (ALD) derived ZrO2 overcoat can effectively suppress the Sr-segregation by reducing the surface concentration of oxygen vacancies. Electrochemical impedance spectroscopy (EIS) study further confirms that the ALD-ZrO2-coated LSCo epitaxial film exhibits a much lower and more stable polarization resistance than the uncoated one at 550 °C for >300 hours, suggesting that Sr-segregation is the source of the higher resistance.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of South Carolina, Columbia, SC (United States). Dept. of Mechanical Engineering
  2. Univ. of South Carolina, Columbia, SC (United States). Dept. of Mechanical Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Sciences and Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Sciences and Technology Division
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1491297
Alternate Identifier(s):
OSTI ID: 1482846; OSTI ID: 1656484
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; DMR-1464112
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 47; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wen, Yeting, Yang, Tianrang, Lee, Dongkyu, Lee, Ho Nyung, Crumlin, Ethan J., and Huang, Kevin. Temporal and thermal evolutions of surface Sr-segregation in pristine and atomic layer deposition modified La0.6Sr0.4CoO3-δ epitaxial films. United States: N. p., 2018. Web. doi:10.1039/c8ta08355j.
Wen, Yeting, Yang, Tianrang, Lee, Dongkyu, Lee, Ho Nyung, Crumlin, Ethan J., & Huang, Kevin. Temporal and thermal evolutions of surface Sr-segregation in pristine and atomic layer deposition modified La0.6Sr0.4CoO3-δ epitaxial films. United States. doi:10.1039/c8ta08355j.
Wen, Yeting, Yang, Tianrang, Lee, Dongkyu, Lee, Ho Nyung, Crumlin, Ethan J., and Huang, Kevin. Fri . "Temporal and thermal evolutions of surface Sr-segregation in pristine and atomic layer deposition modified La0.6Sr0.4CoO3-δ epitaxial films". United States. doi:10.1039/c8ta08355j. https://www.osti.gov/servlets/purl/1491297.
@article{osti_1491297,
title = {Temporal and thermal evolutions of surface Sr-segregation in pristine and atomic layer deposition modified La0.6Sr0.4CoO3-δ epitaxial films},
author = {Wen, Yeting and Yang, Tianrang and Lee, Dongkyu and Lee, Ho Nyung and Crumlin, Ethan J. and Huang, Kevin},
abstractNote = {The bulk-to-surface Sr segregation can seriously compromise the stability of oxygen electrocatalysis in La1-xSrxCoO3-δ and limit its practical applications such as in solid oxide fuel cells. In this work, we show via in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) that the surface Sr-segregation is a kinetically fast process and the equilibrium surface Sr-concentration follows Arrhenius law from 250 to 520 °C at a fixed pO2 = 1 × 10-3 atm. Furthermore, we also show that application of a nanoscaled, atomic layer deposition (ALD) derived ZrO2 overcoat can effectively suppress the Sr-segregation by reducing the surface concentration of oxygen vacancies. Electrochemical impedance spectroscopy (EIS) study further confirms that the ALD-ZrO2-coated LSCo epitaxial film exhibits a much lower and more stable polarization resistance than the uncoated one at 550 °C for >300 hours, suggesting that Sr-segregation is the source of the higher resistance.},
doi = {10.1039/c8ta08355j},
journal = {Journal of Materials Chemistry. A},
number = 47,
volume = 6,
place = {United States},
year = {2018},
month = {11}
}

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Works referenced in this record:

Enhanced Oxygen Surface Exchange Kinetics and Stability on Epitaxial La 0.8 Sr 0.2 CoO 3−δ Thin Films by La 0.8 Sr 0.2 MnO 3−δ Decoration
journal, June 2014

  • Lee, Dongkyu; Lee, Yueh-Lin; Grimaud, Alexis
  • The Journal of Physical Chemistry C, Vol. 118, Issue 26
  • DOI: 10.1021/jp502192m

Relationship between Cation Segregation and the Electrochemical Oxygen Reduction Kinetics of La0.6Sr0.4CoO3−δ Thin Film Electrodes
journal, January 2011

  • Kubicek, Markus; Limbeck, Andreas; Frömling, Till
  • Journal of The Electrochemical Society, Vol. 158, Issue 6
  • DOI: 10.1149/1.3581114

Photoelectron spectroscopy under ambient pressure and temperature conditions
journal, March 2009

  • Frank Ogletree, D.; Bluhm, Hendrik; Hebenstreit, Eleonore D.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2
  • DOI: 10.1016/j.nima.2008.12.155

Electrochemical performance and degradation of (La0.6Sr0.4)0.99CoO3−δ as porous SOFC-cathode
journal, September 2008

  • Hjalmarsson, Per; Søgaard, Martin; Mogensen, Mogens
  • Solid State Ionics, Vol. 179, Issue 27-32
  • DOI: 10.1016/j.ssi.2007.11.010

Oxygen exchange kinetics on a highly oriented La0.5Sr0.5CoO3−δ thin film prepared by pulsed-laser deposition
journal, August 2001

  • Yang, Yuemei L.; Jacobson, A. J.; Chen, C. L.
  • Applied Physics Letters, Vol. 79, Issue 6
  • DOI: 10.1063/1.1390316

La2Zr2O7 formation and oxygen reduction kinetics of the La0.85Sr0.15MnyO3, O2(g)|YSZ system
journal, September 1998


Stretching Epitaxial La 0.6 Sr 0.4 CoO 3−δ for Fast Oxygen Reduction
journal, November 2017

  • Lee, Dongkyu; Jacobs, Ryan; Jee, Youngseok
  • The Journal of Physical Chemistry C, Vol. 121, Issue 46
  • DOI: 10.1021/acs.jpcc.7b06374

Surface strontium enrichment on highly active perovskites for oxygen electrocatalysis in solid oxide fuel cells
journal, January 2012

  • Crumlin, Ethan J.; Mutoro, Eva; Liu, Zhi
  • Energy & Environmental Science, Vol. 5, Issue 3
  • DOI: 10.1039/c2ee03397f

Resistive Switching Properties and Failure Behaviors of (Pt, Cu)/Amorphous ZrO2/Pt Sandwich Structures
journal, July 2016

  • Zhai, Haifa; Kong, Jizhou; Yang, Jien
  • Journal of Materials Science & Technology, Vol. 32, Issue 7
  • DOI: 10.1016/j.jmst.2016.03.011

In situ characterization of strontium surface segregation in epitaxial La0.7Sr0.3MnO3 thin films as a function of oxygen partial pressure
journal, October 2008

  • Fister, Tim T.; Fong, Dillon D.; Eastman, Jeffrey A.
  • Applied Physics Letters, Vol. 93, Issue 15
  • DOI: 10.1063/1.2987731

Water Reactivity on the LaCoO 3 (001) Surface: An Ambient Pressure X-ray Photoelectron Spectroscopy Study
journal, August 2014

  • Stoerzinger, Kelsey A.; Hong, Wesley T.; Crumlin, Ethan J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp502970r

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Comparison of oxygen exchange kinetics of the IT-SOFC cathode materials La0.5Sr0.5CoO3−δ and La0.6Sr0.4CoO3−δ
journal, October 2012


Impact of Sr segregation on the electronic structure and oxygen reduction activity of SrTi1−xFexO3 surfaces
journal, January 2012

  • Chen, Yan; Jung, WooChul; Cai, Zhuhua
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee21463f

Investigation of surface Sr segregation in model thin film solid oxidefuel cell perovskite electrodes
journal, January 2012

  • Jung, WooChul; Tuller, Harry L.
  • Energy Environ. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C1EE02762J

In Situ Studies of the Temperature-Dependent Surface Structure and Chemistry of Single-Crystalline (001)-Oriented La 0.8 Sr 0.2 CoO 3−δ Perovskite Thin Films
journal, April 2013

  • Feng, Zhenxing; Crumlin, Ethan J.; Hong, Wesley T.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz400250t

Electrochemically driven cation segregation in the mixed conductor La0.6Sr0.4Co0.2Fe0.8O3−δ
journal, March 2012


Oxygen surface exchange kinetics and stability of (La,Sr) 2 CoO 4±δ /La 1−x Sr x MO 3−δ (M = Co and Fe) hetero-interfaces at intermediate temperatures
journal, January 2015

  • Lee, Dongkyu; Lee, Yueh-Lin; Hong, Wesley T.
  • Journal of Materials Chemistry A, Vol. 3, Issue 5
  • DOI: 10.1039/C4TA05795C

Atomistic simulations of surface segregation of defects in solid oxide electrolytes
journal, April 2010


Impedance Studies of Oxygen Exchange on Dense Thin Film Electrodes of La[sub 0.5]Sr[sub 0.5]CoO[sub 3−δ]
journal, January 2000

  • Yang, Y. L.; Chen, C. L.; Chen, S. Y.
  • Journal of The Electrochemical Society, Vol. 147, Issue 11
  • DOI: 10.1149/1.1394010

Enhanced oxygen reduction activity on surface-decorated perovskite thin films for solid oxide fuel cells
journal, January 2011

  • Mutoro, Eva; Crumlin, Ethan J.; Biegalski, Michael D.
  • Energy & Environmental Science, Vol. 4, Issue 9, p. 3689-3696
  • DOI: 10.1039/c1ee01245b

Stabilizing Nanostructured Solid Oxide Fuel Cell Cathode with Atomic Layer Deposition
journal, August 2013

  • Gong, Yunhui; Palacio, Diego; Song, Xueyan
  • Nano Letters, Vol. 13, Issue 9
  • DOI: 10.1021/nl402138w

Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface
journal, June 2016

  • Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin
  • Nature Materials, Vol. 15, Issue 9
  • DOI: 10.1038/nmat4659

Oxygen Electrocatalysis on Epitaxial La 0.6 Sr 0.4 CoO 3- δ Perovskite Thin Films for Solid Oxide Fuel Cells
journal, January 2012

  • Crumlin, Ethan J.; Ahn, Sung-Jin; Lee, Dongkyu
  • Journal of The Electrochemical Society, Vol. 159, Issue 7
  • DOI: 10.1149/2.018207jes

Cation diffusion in La0.6Sr0.4CoO3−δ below 800 °C and its relevance for Sr segregation
journal, January 2014

  • Kubicek, Markus; Rupp, Ghislain M.; Huber, Stefanie
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 6
  • DOI: 10.1039/c3cp51906f

Impedance spectroscopic study on well-defined (La,Sr)(Co,Fe)O3−δ model electrodes
journal, April 2006


Cation Size Mismatch and Charge Interactions Drive Dopant Segregation at the Surfaces of Manganite Perovskites
journal, May 2013

  • Lee, Wonyoung; Han, Jeong Woo; Chen, Yan
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja3125349

Sr diffusion in undoped and La-doped SrTiO 3 single crystals under oxidizing conditions
journal, January 2005

  • Gömann, Karsten; Borchardt, Günter; Schulz, Michał
  • Phys. Chem. Chem. Phys., Vol. 7, Issue 9
  • DOI: 10.1039/B418824A

Systematic XPS studies of metal oxides, hydroxides and peroxides
journal, January 2000

  • Dupin, Jean-Charles; Gonbeau, Danielle; Vinatier, Philippe
  • Physical Chemistry Chemical Physics, Vol. 2, Issue 6
  • DOI: 10.1039/a908800h

New ambient pressure photoemission endstation at Advanced Light Source beamline 9.3.2
journal, May 2010

  • Grass, Michael E.; Karlsson, Patrik G.; Aksoy, Funda
  • Review of Scientific Instruments, Vol. 81, Issue 5
  • DOI: 10.1063/1.3427218

Systematic x-ray photoelectron spectroscopic study of La1?xSrx-based perovskite-type oxides
journal, January 2002

  • van der Heide, P. A. W.
  • Surface and Interface Analysis, Vol. 33, Issue 5
  • DOI: 10.1002/sia.1227

Electrical Conductivity and Seebeck Coefficient of Nonstoichiometric La[sub 1−x]Sr[sub x]CoO[sub 3−δ]
journal, January 1989

  • Mizusaki, Junichiro
  • Journal of The Electrochemical Society, Vol. 136, Issue 7
  • DOI: 10.1149/1.2097187

Crystal structure, electrical and magnetic properties of La1 − xSrxCoO3 − y
journal, September 1995


Effect of atmospheric CO2 on surface segregation and phase formation in La0.6Sr0.4Co0.2Fe0.8O3− thin films
journal, December 2014


Enhancing SOFC cathode performance by surface modification through infiltration
journal, January 2014

  • Ding, Dong; Li, Xiaxi; Lai, Samson Yuxiu
  • Energy & Environmental Science, Vol. 7, Issue 2
  • DOI: 10.1039/c3ee42926a

    Works referencing / citing this record:

    Nanostructured Materials and Interfaces for Advanced Ionic Electronic Conducting Oxides
    journal, May 2019

    • Acosta, Matias; Baiutti, Federico; Tarancón, Albert
    • Advanced Materials Interfaces, Vol. 6, Issue 15
    • DOI: 10.1002/admi.201900462

    Heterointerface engineering for enhancing the electrochemical performance of solid oxide cells
    journal, January 2020

    • Zhao, Chenhuan; Li, Yifeng; Zhang, Wenqiang
    • Energy & Environmental Science, Vol. 13, Issue 1
    • DOI: 10.1039/c9ee02230a