DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enhancing Oxygen Exchange Activity by Tailoring Perovskite Surfaces

Abstract

A detailed understanding of the effects of surface chemical and geometric composition is essential for understanding the electrochemical performance of the perovskite (ABO3) oxides commonly used as electrocatalysts in the cathodes of ceramic fuel cells. In this work, we report how the addition of submonolayer quantities of A- and B-site cations affect the rate of the Oxygen Reduction Reaction (ORR) of Sr-doped LaFeO3 (LSF), LaMnO3 (LSM), and LaCoO3 (LSCo). Density functional theory (DFT) calculations were performed to determine the stability of different active sites on a collection of surfaces. With LSF and LSM, rates for ORR are significantly higher on the A-site terminated surface, while surface termination is less important for LSCo. Our findings highlight the importance of tailoring the surface termination of the perovskite to obtain its ultimate ORR performance.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1594019
Grant/Contract Number:  
FE0031252
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 10; Journal Issue: 14; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxygen reduction reaction; electrocatalysis; cathode; solid oxide fuel cells

Citation Formats

Cheng, Yuan, Raman, Abhinav S., Paige, Julian, Zhang, Liang, Sun, Danyi, Chen, Mavis U., Vojvodic, Aleksandra, Gorte, Raymond J., and Vohs, John M. Enhancing Oxygen Exchange Activity by Tailoring Perovskite Surfaces. United States: N. p., 2019. Web. doi:10.1021/acs.jpclett.9b01235.
Cheng, Yuan, Raman, Abhinav S., Paige, Julian, Zhang, Liang, Sun, Danyi, Chen, Mavis U., Vojvodic, Aleksandra, Gorte, Raymond J., & Vohs, John M. Enhancing Oxygen Exchange Activity by Tailoring Perovskite Surfaces. United States. https://doi.org/10.1021/acs.jpclett.9b01235
Cheng, Yuan, Raman, Abhinav S., Paige, Julian, Zhang, Liang, Sun, Danyi, Chen, Mavis U., Vojvodic, Aleksandra, Gorte, Raymond J., and Vohs, John M. Thu . "Enhancing Oxygen Exchange Activity by Tailoring Perovskite Surfaces". United States. https://doi.org/10.1021/acs.jpclett.9b01235. https://www.osti.gov/servlets/purl/1594019.
@article{osti_1594019,
title = {Enhancing Oxygen Exchange Activity by Tailoring Perovskite Surfaces},
author = {Cheng, Yuan and Raman, Abhinav S. and Paige, Julian and Zhang, Liang and Sun, Danyi and Chen, Mavis U. and Vojvodic, Aleksandra and Gorte, Raymond J. and Vohs, John M.},
abstractNote = {A detailed understanding of the effects of surface chemical and geometric composition is essential for understanding the electrochemical performance of the perovskite (ABO3) oxides commonly used as electrocatalysts in the cathodes of ceramic fuel cells. In this work, we report how the addition of submonolayer quantities of A- and B-site cations affect the rate of the Oxygen Reduction Reaction (ORR) of Sr-doped LaFeO3 (LSF), LaMnO3 (LSM), and LaCoO3 (LSCo). Density functional theory (DFT) calculations were performed to determine the stability of different active sites on a collection of surfaces. With LSF and LSM, rates for ORR are significantly higher on the A-site terminated surface, while surface termination is less important for LSCo. Our findings highlight the importance of tailoring the surface termination of the perovskite to obtain its ultimate ORR performance.},
doi = {10.1021/acs.jpclett.9b01235},
journal = {Journal of Physical Chemistry Letters},
number = 14,
volume = 10,
place = {United States},
year = {Thu Jul 04 00:00:00 EDT 2019},
month = {Thu Jul 04 00:00:00 EDT 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Schematic showing the different ALD-modified surfaces that were investigated in this study.

Save / Share:

Works referenced in this record:

Mechanism of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 cathode degradation
journal, July 2012

  • Oh, Dongjo; Gostovic, Danijel; Wachsman, Eric D.
  • Journal of Materials Research, Vol. 27, Issue 15
  • DOI: 10.1557/jmr.2012.222

Surface Strontium Segregation of Solid Oxide Fuel Cell Cathodes Proved by In Situ Depth-Resolved X-ray Absorption Spectroscopy
journal, January 2014

  • Orikasa, Y.; Crumlin, E. J.; Sako, S.
  • ECS Electrochemistry Letters, Vol. 3, Issue 4
  • DOI: 10.1149/2.006404eel

Surface composition of perovskite-type materials studied by Low Energy Ion Scattering (LEIS)
journal, September 2014


Modification of SOFC Cathodes by Atomic Layer Deposition
journal, January 2013

  • Yu, Anthony S.; Küngas, Rainer; Vohs, John M.
  • Journal of The Electrochemical Society, Vol. 160, Issue 11
  • DOI: 10.1149/2.045311jes

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

Surface Tuning of Solid Oxide Fuel Cell Cathode by Atomic Layer Deposition
journal, October 2018

  • Choi, Hyung Jong; Bae, Kiho; Grieshammer, Steffen
  • Advanced Energy Materials, Vol. 8, Issue 33
  • DOI: 10.1002/aenm.201802506

Real-time impedance monitoring of oxygen reduction during surface modification of thin film cathodes
journal, March 2017

  • Rupp, Ghislain M.; Opitz, Alexander K.; Nenning, Andreas
  • Nature Materials, Vol. 16, Issue 6
  • DOI: 10.1038/nmat4879

Modification of LSF-YSZ Composite Cathodes by Atomic Layer Deposition
journal, January 2017

  • Rahmanipour, M.; Cheng, Y.; Onn, T. M.
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.0181709jes

Preparation of SOFC Cathodes by Infiltration into LSF-YSZ Composite Scaffolds
journal, November 2015

  • Cheng, Yuan; Yu, Anthony S.; Li, Xiaoyan
  • Journal of The Electrochemical Society, Vol. 163, Issue 2
  • DOI: 10.1149/2.0171602jes

SOFC Cathodes Prepared by Infiltration with Various LSM Precursors
journal, January 2006

  • Huang, Y.; Vohs, J. M.; Gorte, R. J.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 5, p. A237-A240
  • DOI: 10.1149/1.2183867

Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods
journal, March 2003


Sr Segregation in Perovskite Oxides: Why It Happens and How It Exists
journal, August 2018


Degradation Mechanisms of La–Sr–Co–Fe–O[sub 3] SOFC Cathodes
journal, January 2006

  • Simner, S. P.; Anderson, M. D.; Engelhard, M. H.
  • Electrochemical and Solid-State Letters, Vol. 9, Issue 10
  • DOI: 10.1149/1.2266160

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

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

Ab initio energetics of La B O 3 ( 001 ) ( B = Mn , Fe, Co, and Ni) for solid oxide fuel cell cathodes
journal, December 2009


Pathways for Oxygen Incorporation in Mixed Conducting Perovskites: A DFT-Based Mechanistic Analysis for (La, Sr)MnO 3−δ
journal, January 2010

  • Mastrikov, Yuri A.; Merkle, Rotraut; Heifets, Eugene
  • The Journal of Physical Chemistry C, Vol. 114, Issue 7
  • DOI: 10.1021/jp909401g

Nonstoichiometry and defect structure of the perovskite-type oxides La1−xSrxFeO3−°
journal, July 1985

  • Mizusaki, Junichiro; Yoshihiro, Masafumi; Yamauchi, Shigeru
  • Journal of Solid State Chemistry, Vol. 58, Issue 2
  • DOI: 10.1016/0022-4596(85)90243-9

Quantum-mechanics-based design principles for solid oxide fuel cell cathode materials
journal, January 2011

  • Pavone, Michele; Ritzmann, Andrew M.; Carter, Emily A.
  • Energy & Environmental Science, Vol. 4, Issue 12
  • DOI: 10.1039/c1ee02377b

Characterization of LSM-YSZ Composites Prepared by Impregnation Methods
journal, January 2005

  • Huang, Yingyi; Vohs, John M.; Gorte, Raymond J.
  • Journal of The Electrochemical Society, Vol. 152, Issue 7
  • DOI: 10.1149/1.1926669

Cathode materials for solid oxide fuel cells: a review
journal, October 2009

  • Sun, Chunwen; Hui, Rob; Roller, Justin
  • Journal of Solid State Electrochemistry, Vol. 14, Issue 7
  • DOI: 10.1007/s10008-009-0932-0

High-Performance SOFC Cathodes Prepared by Infiltration
journal, March 2009


Modeling Impedance Response of SOFC Cathodes Prepared by Infiltration
journal, January 2011

  • Bidrawn, F.; Küngas, R.; Vohs, J. M.
  • Journal of The Electrochemical Society, Vol. 158, Issue 5
  • DOI: 10.1149/1.3565174

Oxygen nonstoichiometry and transport properties of strontium substituted lanthanum ferrite
journal, April 2007

  • Søgaard, Martin; Vang Hendriksen, Peter; Mogensen, Mogens
  • Journal of Solid State Chemistry, Vol. 180, Issue 4
  • DOI: 10.1016/j.jssc.2007.02.012

Nonstoichiometry of the perovskite-type oxides La1−xSrxCoO3−δ
journal, May 1989


Oxygen nonstoichiometry and defect equilibrium in the perovskite-type oxides La1−xSrxMnO3+d
journal, April 2000


Catalysis in Solid Oxide Fuel Cells
journal, July 2011


Surface composition of perovskite-type materials studied by Low Energy Ion Scattering (LEIS)
journal, September 2014


Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods
journal, March 2003


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.