The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites
Abstract
Optimizing proton conduction in solids remains the most promising solution for achieving intermediate temperature (~750–1000 K) solid oxide fuel cell devices, and enabling selective membranes for H2 separation. Proton conduction, a thermally activated process, exhibits its highest rates in yttrium (Y) acceptor doped BaZrO3 at an optimal doping level of 20% Y. The presence of extended defects such as grain boundaries has typically generated a wide variability in reported conductivity values. This has hindered a fundamental mechanistic understanding of how (acceptor) doping levels correlate with the activation energy of protons to produce an optimal doping level for fast proton transport. While isolated dopants have been suggested as the primary source of proton trapping, our results indicate that it is the local dopant-density that matters. Here in this work, we show that increasing the local dopant density promotes localized lattice distortions in the presence of point defects such as oxygen-vacancies or proton interstitials. An increasing distortion amplitude traps the point defects more strongly in the form of polarons, forming defect-clusters at higher concentrations. This leads to a monotonic increase in the activation energy (and hence a decrease in proton mobility) as observed in our measurements. The optimum doping level can nowmore »
- Authors:
-
[1];
[2];
[2];
[3];
[4];
[5];
[6];
[2];
[2];
[2];
[2]
- Georgia Inst. of Technology, Atlanta, GA (United States). Department of Materials Science and Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
- Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Material Science and Technology Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Science
- Georgia Inst. of Technology, Atlanta, GA (United States). Department of Materials Science and Engineering and The George Woodruff School of Mechanical Engineering
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1470906
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 30; Journal Issue: 15; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Ding, Jilai, Balachandran, Janakiraman, Sang, Xiahan, Guo, Wei, Anchell, Jonathan S., Veith, Gabriel M., Bridges, Craig A., Cheng, Yongqiang, Rouleau, Christopher M., Poplawsky, Jonathan D., Bassiri-Gharb, Nazanin, Unocic, Raymond R., and Ganesh, P. The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b00502.
Ding, Jilai, Balachandran, Janakiraman, Sang, Xiahan, Guo, Wei, Anchell, Jonathan S., Veith, Gabriel M., Bridges, Craig A., Cheng, Yongqiang, Rouleau, Christopher M., Poplawsky, Jonathan D., Bassiri-Gharb, Nazanin, Unocic, Raymond R., & Ganesh, P. The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites. United States. https://doi.org/10.1021/acs.chemmater.8b00502
Ding, Jilai, Balachandran, Janakiraman, Sang, Xiahan, Guo, Wei, Anchell, Jonathan S., Veith, Gabriel M., Bridges, Craig A., Cheng, Yongqiang, Rouleau, Christopher M., Poplawsky, Jonathan D., Bassiri-Gharb, Nazanin, Unocic, Raymond R., and Ganesh, P. Wed .
"The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites". United States. https://doi.org/10.1021/acs.chemmater.8b00502. https://www.osti.gov/servlets/purl/1470906.
@article{osti_1470906,
title = {The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites},
author = {Ding, Jilai and Balachandran, Janakiraman and Sang, Xiahan and Guo, Wei and Anchell, Jonathan S. and Veith, Gabriel M. and Bridges, Craig A. and Cheng, Yongqiang and Rouleau, Christopher M. and Poplawsky, Jonathan D. and Bassiri-Gharb, Nazanin and Unocic, Raymond R. and Ganesh, P.},
abstractNote = {Optimizing proton conduction in solids remains the most promising solution for achieving intermediate temperature (~750–1000 K) solid oxide fuel cell devices, and enabling selective membranes for H2 separation. Proton conduction, a thermally activated process, exhibits its highest rates in yttrium (Y) acceptor doped BaZrO3 at an optimal doping level of 20% Y. The presence of extended defects such as grain boundaries has typically generated a wide variability in reported conductivity values. This has hindered a fundamental mechanistic understanding of how (acceptor) doping levels correlate with the activation energy of protons to produce an optimal doping level for fast proton transport. While isolated dopants have been suggested as the primary source of proton trapping, our results indicate that it is the local dopant-density that matters. Here in this work, we show that increasing the local dopant density promotes localized lattice distortions in the presence of point defects such as oxygen-vacancies or proton interstitials. An increasing distortion amplitude traps the point defects more strongly in the form of polarons, forming defect-clusters at higher concentrations. This leads to a monotonic increase in the activation energy (and hence a decrease in proton mobility) as observed in our measurements. The optimum doping level can now be explained as a competition between increasing proton concentration with doping levels and increasing activation energy due to defect-clusters formed by defect-polarons. Based on our findings, we demonstrate how to improve proton conductivity in doped BaZrO3, by inhibiting this dopant-lattice polaronic interaction. Finally, this approach should be generally applicable for ionic conduction in perovskite oxides such as oxygen-ion conduction in solid-oxide fuel cells and alkali-ion conduction in solid-state batteries where carriers might get trapped as defect-polarons.},
doi = {10.1021/acs.chemmater.8b00502},
journal = {Chemistry of Materials},
number = 15,
volume = 30,
place = {United States},
year = {Wed Jun 27 00:00:00 EDT 2018},
month = {Wed Jun 27 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 26 works
Citation information provided by
Web of Science
Web of Science
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:
Proton-Conducting Oxides
journal, August 2003
- Kreuer, K. D.
- Annual Review of Materials Research, Vol. 33, Issue 1, p. 333-359
High proton conduction in grain-boundary-free yttrium-doped barium zirconate films grown by pulsed laser deposition
journal, September 2010
- Pergolesi, Daniele; Fabbri, Emiliana; D’Epifanio, Alessandra
- Nature Materials, Vol. 9, Issue 10
Does the increase in Y-dopant concentration improve the proton conductivity of BaZr1−xYxO3−δ fuel cell electrolytes?
journal, July 2010
- Fabbri, Emiliana; Pergolesi, Daniele; Licoccia, Silvia
- Solid State Ionics, Vol. 181, Issue 21-22
Effect of crystallinity on proton conductivity in yttrium-doped barium zirconate thin films
journal, September 2011
- Kim, Young Beom; Gür, Turgut M.; Jung, Hee-Joon
- Solid State Ionics, Vol. 198, Issue 1
Processing of yttrium-doped barium zirconate for high proton conductivity
journal, May 2007
- Babilo, Peter; Uda, Tetsuya; Haile, Sossina M.
- Journal of Materials Research, Vol. 22, Issue 5
Electrical Conductivity of the High-Temperature Proton Conductor BaZr0.9Y0.1O2.95
journal, April 2000
- Bohn, Hans G.; Schober, Tilman
- Journal of the American Ceramic Society, Vol. 83, Issue 4
Microstructures and grain boundary conductivity of BaZr1−xYxO3 (x=0.05, 0.10, 0.15) ceramics
journal, April 2007
- Iguchi, F.; Sata, N.; Tsurui, T.
- Solid State Ionics, Vol. 178, Issue 7-10
Effect of acceptor dopants on the proton mobility in : A density functional investigation
journal, August 2007
- Björketun, Mårten E.; Sundell, Per G.; Wahnström, Göran
- Physical Review B, Vol. 76, Issue 5
Proton trapping in yttrium-doped barium zirconate
journal, May 2013
- Yamazaki, Yoshihiro; Blanc, Frédéric; Okuyama, Yuji
- Nature Materials, Vol. 12, Issue 7
Enthalpy of formation and thermodynamic insights into yttrium doped BaZrO 3
journal, January 2014
- Gonçalves, M. D.; Maram, P. S.; Muccillo, R.
- J. Mater. Chem. A, Vol. 2, Issue 42
Proton Diffusion in Perovskite-Type Oxides Based on Small Polaron Model
journal, November 2005
- Tomoyose, Tomozo; Shimoji, Nobuaki; Wakamura, Kunio
- Journal of the Physical Society of Japan, Vol. 74, Issue 11
Relaxation Modes of Classical Hopping Protons in Perovskite Structures I
journal, January 2004
- Ishii, Tadao; Ichigozaki, Atsushi
- Journal of the Physical Society of Japan, Vol. 73, Issue 1
Polaronic contributions to oxidation and hole conductivity in acceptor-doped
journal, August 2016
- Lindman, Anders; Erhart, Paul; Wahnström, Göran
- Physical Review B, Vol. 94, Issue 7
Experimental neutron scattering evidence for proton polaron in hydrated metal oxide proton conductors
journal, June 2017
- Braun, Artur; Chen, Qianli
- Nature Communications, Vol. 8, Issue 1
Transport in Proton Conductors for Fuel-Cell Applications: Simulations, Elementary Reactions, and Phenomenology
journal, October 2004
- Kreuer, Klaus-Dieter; Paddison, Stephen J.; Spohr, Eckhard
- Chemical Reviews, Vol. 104, Issue 10
Materials for Solid Oxide Fuel Cells †
journal, February 2010
- Jacobson, Allan J.
- Chemistry of Materials, Vol. 22, Issue 3
Design principles for solid-state lithium superionic conductors
journal, August 2015
- Wang, Yan; Richards, William Davidson; Ong, Shyue Ping
- Nature Materials, Vol. 14, Issue 10
Strongly correlated perovskite fuel cells
journal, May 2016
- Zhou, You; Guan, Xiaofei; Zhou, Hua
- Nature, Vol. 534, Issue 7606
Perovskite nickelates as electric-field sensors in salt water
journal, December 2017
- Zhang, Zhen; Schwanz, Derek; Narayanan, Badri
- Nature, Vol. 553, Issue 7686
Habituation based synaptic plasticity and organismic learning in a quantum perovskite
journal, August 2017
- Zuo, Fan; Panda, Priyadarshini; Kotiuga, Michele
- Nature Communications, Vol. 8, Issue 1
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Defect Genome of Cubic Perovskites for Fuel Cell Applications
journal, November 2017
- Balachandran, Janakiraman; Lin, Lianshan; Anchell, Jonathan S.
- The Journal of Physical Chemistry C, Vol. 121, Issue 48
Spatially Resolved Probing of Electrochemical Reactions via Energy Discovery Platforms
journal, June 2015
- Ding, Jilai; Strelcov, Evgheni; Kalinin, Sergei V.
- Nano Letters, Vol. 15, Issue 6
Electrochemical Properties and Intermediate-Temperature Fuel Cell Performance of Dense Yttrium-Doped Barium Zirconate with Calcium Addition
journal, August 2011
- Sun, Ziqi; Fabbri, Emiliana; Bi, Lei
- Journal of the American Ceramic Society, Vol. 95, Issue 2
Heavily strained BaZr 0.8 Y 0.2 O 3−x interfaces with enhanced transport properties
journal, February 2014
- Foglietti, Vittorio; Yang, Nan; Tebano, Antonello
- Applied Physics Letters, Vol. 104, Issue 8
On the proton conductivity in pure and gadolinium doped nanocrystalline cerium oxide
journal, January 2011
- Shirpour, Mona; Gregori, Giuliano; Merkle, Rotraut
- Phys. Chem. Chem. Phys., Vol. 13, Issue 3
Atom Probe Tomography of Yttrium-Doped Barium-Cerium-Zirconium Oxide with NiO Addition
journal, July 2014
- Diercks, David R.; Gorman, Brian P.; Manerbino, Anthony
- Journal of the American Ceramic Society, Vol. 97, Issue 10
Small polarons and point defects in barium cerate
journal, December 2015
- Swift, Michael; Janotti, Anderson; Van de Walle, Chris G.
- Physical Review B, Vol. 92, Issue 21
On the structural origins of ferroelectricity in HfO 2 thin films
journal, April 2015
- Sang, Xiahan; Grimley, Everett D.; Schenk, Tony
- Applied Physics Letters, Vol. 106, Issue 16
Effect of Dopant–Host Ionic Radii Mismatch on Acceptor-Doped Barium Zirconate Microstructure and Proton Conductivity
journal, April 2017
- Gilardi, Elisa; Fabbri, Emiliana; Bi, Lei
- The Journal of Physical Chemistry C, Vol. 121, Issue 18
Defect and Dopant Properties of the SrCeO 3 -Based Proton Conductor
journal, April 2005
- Mather, Glenn C.; Islam, M. Saiful
- Chemistry of Materials, Vol. 17, Issue 7
Alkali metals as efficient A-site acceptor dopants in proton conducting BaZrO 3
journal, January 2016
- Løken, Andreas; Saeed, Sarmad W.; Getz, Marit N.
- Journal of Materials Chemistry A, Vol. 4, Issue 23
Works referencing / citing this record:
Preferential proton conduction along a three-dimensional dopant network in yttrium-doped barium zirconate: a first-principles study
journal, January 2018
- Toyoura, Kazuaki; Meng, Weijie; Han, Donglin
- Journal of Materials Chemistry A, Vol. 6, Issue 45
Superior electrocatalytic hydrogen evolution at engineered non-stoichiometric two-dimensional transition metal dichalcogenide edges
journal, January 2019
- Hu, Guoxiang; Fung, Victor; Sang, Xiahan
- Journal of Materials Chemistry A, Vol. 7, Issue 31