Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy

Abstract

Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at -20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (~30 nm in diameter) inside a ceria grain is reduced to the C-type CeO1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO2, Ce0.94Sm0.06O1.97, Ce0.89Sm0.11O1.945, and Ce0.8Sm0.2O1.9, respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT)more » calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [3]
+ Show Author Affiliations
  1. Georgia Institute of Technology, Atlanta, GA (United States)
  2. National Chiao Tung Univ., Hsinchu (Taiwan)
  3. Georgia Institute of Technology, Atlanta, GA (United States); Chinese Academy of Sciences (CAS), Beijing (China)
Publication Date:
Research Org.:
Georgia Institute of Technology, Atlanta, GA (United States); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1799503
Alternate Identifier(s):
OSTI ID: 1661708
Grant/Contract Number:  
EE0008439; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Materials Today
Additional Journal Information:
Journal Volume: 38; Journal Issue: C; Journal ID: ISSN 1369-7021
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials Science

Citation Formats

Ding, Yong, Choi, YongMan, Chen, Yu, Pradel, Ken C., Liu, Meilin, and Wang, Zhong Lin. Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy. United States: N. p., 2020. Web. doi:10.1016/j.mattod.2020.04.006.
Copy to clipboard
Ding, Yong, Choi, YongMan, Chen, Yu, Pradel, Ken C., Liu, Meilin, & Wang, Zhong Lin. Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy. United States. https://doi.org/10.1016/j.mattod.2020.04.006
Copy to clipboard
Ding, Yong, Choi, YongMan, Chen, Yu, Pradel, Ken C., Liu, Meilin, and Wang, Zhong Lin. Tue . "Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy". United States. https://doi.org/10.1016/j.mattod.2020.04.006. https://www.osti.gov/servlets/purl/1799503.
Copy to clipboard
@article{osti_1799503,
title = {Quantitative nanoscale tracking of oxygen vacancy diffusion inside single ceria grains by in situ transmission electron microscopy},
author = {Ding, Yong and Choi, YongMan and Chen, Yu and Pradel, Ken C. and Liu, Meilin and Wang, Zhong Lin},
abstractNote = {Oxygen vacancy formation and migration in ceria is critical to its electrochemical and catalytic properties in systems for chemical and energy transformation, but its quantification is rather challenging especially at atomic-scale because of disordered distribution. Here we report a rational approach to track oxygen vacancy diffusion in single grains of pure and Sm-doped ceria at -20 °C to 160 °C using in situ (scanning) transmission electron microscopy ((S)TEM). To create a gradient in oxygen vacancy concentration, a small region (~30 nm in diameter) inside a ceria grain is reduced to the C-type CeO1.68 phase by the ionization or radiolysis effect of a high-energy electron beam. The evolution in oxygen vacancy concentration is then mapped through lattice expansion measurement using scanning nano-beam diffraction or 4D STEM at a spatial resolution better than 2 nm; this allows direct determination of local oxygen vacancy diffusion coefficients in a very small domain inside pure and Sm-doped ceria at different temperatures. Further, the activation energies for oxygen transport are determined to be 0.59, 0.66, 1.12, and 1.27 eV for pure CeO2, Ce0.94Sm0.06O1.97, Ce0.89Sm0.11O1.945, and Ce0.8Sm0.2O1.9, respectively, implying that activation energy increases due to impurity scattering. The results are qualitatively supported by density functional theory (DFT) calculations. In addition, our in situ TEM investigation reveals that dislocations impede oxygen vacancy diffusion by absorbing oxygen vacancies from the surrounding areas and pinning them locally. With more oxygen vacancies absorbed, dislocations show extended strain fields with local tensile zone sandwiched between the compressed ones. Therefore, dislocation density should be reduced in order to minimize the resistance to oxygen vacancy diffusion at low temperatures.},
doi = {10.1016/j.mattod.2020.04.006},
journal = {Materials Today},
number = C,
volume = 38,
place = {United States},
year = {Tue Sep 15 00:00:00 EDT 2020},
month = {Tue Sep 15 00:00:00 EDT 2020}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.mattod.2020.04.006
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Oxygen vacancy migration in ceria and Pr-doped ceria: A DFT+U study
journal, March 2010

  • Dholabhai, Pratik P.; Adams, James B.; Crozier, Peter
  • The Journal of Chemical Physics, Vol. 132, Issue 9
  • DOI: 10.1063/1.3327684

Intrinsic and Extrinsic Oxygen Diffusion and Surface Exchange Reaction in Cerium Oxide
journal, January 2000

  • Kamiya, Michiyo; Shimada, Eriko; Ikuma, Yasuro
  • Journal of The Electrochemical Society, Vol. 147, Issue 3
  • DOI: 10.1149/1.1393340

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

A DFT+U study of defect association and oxygen migration in samarium-doped ceria
journal, January 2011

  • Ismail, Arif; Hooper, James; Giorgi, Javier B.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 13
  • DOI: 10.1039/c0cp02062a

Anisotropic Oxygen Ion Diffusion in Layered PrBaCo 2 O 5+δ
journal, December 2011

  • Burriel, Mónica; Peña-Martínez, Juan; Chater, Richard J.
  • Chemistry of Materials, Vol. 24, Issue 3
  • DOI: 10.1021/cm203502s

Projector augmented-wave method
journal, December 1994

Uranium and oxygen self-diffusion in UO2
journal, April 1969

Non-spectroscopic composition measurements of SrTiO 3 -La 0.7 Sr 0.3 MnO 3 multilayers using scanning convergent beam electron diffraction
journal, February 2017

  • Ophus, Colin; Ercius, Peter; Huijben, Mark
  • Applied Physics Letters, Vol. 110, Issue 6
  • DOI: 10.1063/1.4975932

Understanding the ionic conductivity maximum in doped ceria: trapping and blocking
journal, January 2018

  • Koettgen, Julius; Grieshammer, Steffen; Hein, Philipp
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 21
  • DOI: 10.1039/C7CP08535D

Strained Ionic Interfaces: Effect on Oxygen Diffusivity from Atomistic Simulations
journal, February 2014

  • Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 8
  • DOI: 10.1021/jp411277q

Effect of strain on the oxygen diffusion in yttria and gadolinia co-doped ceria
journal, January 2013

Local and transient nanoscale strain mapping during in situ deformation
journal, August 2016

  • Gammer, C.; Kacher, J.; Czarnik, C.
  • Applied Physics Letters, Vol. 109, Issue 8
  • DOI: 10.1063/1.4961683

Strain mapping at nanometer resolution using advanced nano-beam electron diffraction
journal, June 2015

  • Ozdol, V. B.; Gammer, C.; Jin, X. G.
  • Applied Physics Letters, Vol. 106, Issue 25
  • DOI: 10.1063/1.4922994

Dynamic Monte Carlo simulation of spin‐lattice relaxation of quadrupolar nuclei in solids. Oxygen‐17 in yttria‐doped ceria
journal, May 1993

  • Adler, Stuart B.; Smith, Jacob W.; Reimer, Jeffrey A.
  • The Journal of Chemical Physics, Vol. 98, Issue 9
  • DOI: 10.1063/1.464701

Optical Analysis of Oxygen Self-Diffusion in Ultrathin CeO 2 Layers at Low Temperatures
journal, August 2018

  • Neuderth, Paula; Hille, Pascal; Martí-Sánchez, Sara
  • Advanced Energy Materials, Vol. 8, Issue 29
  • DOI: 10.1002/aenm.201802120

A Theoretical Study of Surface Reduction Mechanisms of CeO2(111) and (110) by H2
journal, April 2007

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Molecular dynamics study of oxygen self-diffusion in reduced CeO2
journal, October 2007

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Density functional theory studies of the structure and electronic structure of pure and defective low index surfaces of ceria
journal, February 2005

Diffusion of Oxygen in Ceria at Elevated Temperatures and Its Application to H 2 O/CO 2 Splitting Thermochemical Redox Cycles
journal, February 2014

  • Ackermann, Simon; Scheffe, Jonathan R.; Steinfeld, Aldo
  • The Journal of Physical Chemistry C, Vol. 118, Issue 10
  • DOI: 10.1021/jp500755t

Chemical expansion of nonstoichiometric Pr0.1Ce0.9O2−δ: Correlation with defect equilibrium model
journal, November 2011

First-principles study on defect chemistry and migration of oxide ions in ceria doped with rare-earth cations
journal, January 2009

  • Nakayama, Masanobu; Martin, Manfred
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 17
  • DOI: 10.1039/b900162j

AC Impedance Investigation of Samarium-Doped Ceria
journal, January 2001

  • Zhan, Zhongliang; Wen, Ting-Lian; Tu, Hengyong
  • Journal of The Electrochemical Society, Vol. 148, Issue 5
  • DOI: 10.1149/1.1359198

An evaluation of Ce-Pr oxides and Ce-Pr-Nb oxides mixed conductors for cathodes of solid oxide fuel cells: Structure, thermal expansion and electrical conductivity
journal, January 1994

  • Nauer, Marco; Ftikos, Christos; Steele, Brian C. H.
  • Journal of the European Ceramic Society, Vol. 14, Issue 6
  • DOI: 10.1016/0955-2219(94)90118-X

Self‐Diffusion of Oxygen in Single Crystal and Polycrystalline Aluminum Oxide
journal, August 1960

  • Oishi, Y.; Kingery, W. D.
  • The Journal of Chemical Physics, Vol. 33, Issue 2
  • DOI: 10.1063/1.1731170

Impact of segregation energetics on oxygen conductivity at ionic grain boundaries
journal, January 2014

  • Aidhy, Dilpuneet S.; Zhang, Yanwen; Weber, William J.
  • J. Mater. Chem. A, Vol. 2, Issue 6
  • DOI: 10.1039/C3TA14128D

Oxygen self-diffusion in cerium oxide doped with Nd
journal, January 2001

  • Kamiya, Michiyo; Shimada, Eriko; Ikuma, Yasuro
  • Journal of Materials Research, Vol. 16, Issue 1
  • DOI: 10.1557/JMR.2001.0029

Impact of uniaxial strain and doping on oxygen diffusion in CeO2
journal, August 2014

  • Rushton, M. J. D.; Chroneos, A.
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06068

Strain-Induced Tailoring of Oxygen-Ion Transport in Highly Doped CeO 2 Electrolyte: Effects of Biaxial Extrinsic and Local Lattice Strain
journal, December 2017

  • Ahn, Junsung; Choi, Sungjun; Yoon, Kyung Joong
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 49
  • DOI: 10.1021/acsami.7b13440

Self-diffusion and impurity diffusion in oxides
journal, April 1980

Authors' Response
journal, March 2005

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Small polaron electron transport in reduced CeO2 single crystals
journal, January 1977

Optimization of ionic conductivity in doped ceria
journal, February 2006

  • Andersson, D. A.; Simak, S. I.; Skorodumova, N. V.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 10
  • DOI: 10.1073/pnas.0509537103

Radiation damage in the TEM and SEM
journal, August 2004

Atomic-Resolution Imaging of Oxygen in Perovskite Ceramics
journal, February 2003

A first-principles study on defect association and oxygen ion migration of Sm 3+ and Gd 3+ co-doped ceria
journal, May 2013

The Structures of C–Ce2O3+δ, Ce7O12, and Ce11O20
journal, November 1999

Edge dislocation slows down oxide ion diffusion in doped CeO2 by segregation of charged defects
journal, February 2015

  • Sun, Lixin; Marrocchelli, Dario; Yildiz, Bilge
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7294

Determination of Ce4+/Ce3+ in electron-beam-damaged CeO2 by electron energy-loss spectroscopy
journal, December 1999

Understanding Chemical Expansion in Non-Stoichiometric Oxides: Ceria and Zirconia Case Studies
journal, February 2012

  • Marrocchelli, Dario; Bishop, Sean R.; Tuller, Harry L.
  • Advanced Functional Materials, Vol. 22, Issue 9
  • DOI: 10.1002/adfm.201102648

Defect equilibria and chemical expansion in non-stoichiometric undoped and gadolinium-doped cerium oxide
journal, February 2009

Robust atomic resolution imaging of light elements using scanning transmission electron microscopy
journal, November 2009

  • Findlay, S. D.; Shibata, N.; Sawada, H.
  • Applied Physics Letters, Vol. 95, Issue 19
  • DOI: 10.1063/1.3265946

Electrical properties of ceria-based oxides and their application to solid oxide fuel cells
journal, May 1992

Diffraction contrast imaging using virtual apertures
journal, August 2015

Physical, chemical and electrochemical properties of pure and doped ceria
journal, April 2000

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: