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Cation non-stoichiometry in yttrium-doped barium zirconate: phase behavior, microstructure, and proton conductivity

Yamazaki, Yoshihiro and Hernandez-Sanchez, Raul and Haile, Sossina M. (2010) Cation non-stoichiometry in yttrium-doped barium zirconate: phase behavior, microstructure, and proton conductivity. Journal of Materials Chemistry, 20 (37). pp. 8158-8166. ISSN 0959-9428. https://resolver.caltech.edu/CaltechAUTHORS:20101011-112157948

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Abstract

Recent literature indicates that cation non-stoichiometry in proton-conducting perovskite oxides (ABO_3) can strongly influence their transport properties. Here we have investigated A-site non-stoichiometry in Ba_(1−x)Zr_(0.8)Y_(0.2)O_(3−δ), a candidate electrolyte material for fuel cell and other electrochemical applications. Synthesis is performed using a chemical solution approach in which the barium deficiency is precisely controlled. The perovskite phase is tolerant to barium deficiency up to x = 0.06 as revealed by X-ray diffraction analysis, but accommodates the non-stoichiometry by incorporation of yttrium on the A-site. The dopant partitioning can explain the decrease in cell constant with increasing x, the decrease in proton conductivity (the latter as measured by a.c. impedance spectroscopy under humidified atmosphere), and the decrease in grain size in the sintered compacts. Within the single-phase region barium deficiency also has a detrimental impact on grain boundary conductivity, as a result both of the decreased grain size, leading to a higher number density of grain boundaries and of an increased per boundary resistivity. At higher values of x, a two phase system is observed, with yttria appearing as the predominant secondary phase and the barium zirconate reverting to an undoped composition. From the relative concentrations of the observed phases and their lattice constants, the ternary phase behavior at 1600 °C (the sintering temperature) is generated. Both the bulk and grain boundary conductivities are sharply lower in the two-phase system than in the single phase compositions. The control over processing conditions demonstrates that it is possible to reproducibly prepare large-grained, stoichiometric BaZr_(0.8)Y_(0.2)O_(3−δ) with a total conductivity of 1 × 10^(−2) Scm^(−1) at 450 °C, while revealing the mechanisms by which barium deficiency degrades properties.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c0jm02013cDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2010/JM/c0jm02013cPublisherArticle
ORCID:
AuthorORCID
Haile, Sossina M.0000-0002-5293-6252
Additional Information:© 2010 Royal Society of Chemistry. Received 25th June 2010; Accepted 9th July 2010. This work was supported by the Gordon and Betty Moore Foundation and by JSPS Postdoctoral Fellowships for Research Abroad. Additional support was provided by the National Science Foundation through the Caltech Center for the Science and Engineering of Materials, a Materials Research Science and Engineering Center (DMR-052056). The authors thank Dr Chi Ma for assistance with scanning electron microscopy and electron probe microanalysis.
Funders:
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
NSFDMR-052056
Issue or Number:37
Record Number:CaltechAUTHORS:20101011-112157948
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20101011-112157948
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:20376
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:05 Nov 2010 15:12
Last Modified:03 Oct 2019 02:09

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