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Title: YSZ thin films with minimized grain boundary resistivity

Abstract

In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here in this paper, we report that the ionic conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film–substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grainmore » boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.« less

Authors:
 [1];  [2];  [2];  [3];  [3];  [1];  [1]
  1. Univ. of California, Davis, CA (United States). Dept. of Chemical Engineering and Materials Science
  2. Justus-Liebig-Univ. Gießen, Gießen (Germany). Physikalisch-Chemisches Inst.
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1418491
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 15; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Mills, Edmund M., Kleine-Boymann, Matthias, Janek, Juergen, Yang, Hao, Browning, Nigel D., Takamura, Yayoi, and Kim, Sangtae. YSZ thin films with minimized grain boundary resistivity. United States: N. p., 2016. Web. doi:10.1039/c5cp08032k.
Mills, Edmund M., Kleine-Boymann, Matthias, Janek, Juergen, Yang, Hao, Browning, Nigel D., Takamura, Yayoi, & Kim, Sangtae. YSZ thin films with minimized grain boundary resistivity. United States. doi:10.1039/c5cp08032k.
Mills, Edmund M., Kleine-Boymann, Matthias, Janek, Juergen, Yang, Hao, Browning, Nigel D., Takamura, Yayoi, and Kim, Sangtae. Thu . "YSZ thin films with minimized grain boundary resistivity". United States. doi:10.1039/c5cp08032k. https://www.osti.gov/servlets/purl/1418491.
@article{osti_1418491,
title = {YSZ thin films with minimized grain boundary resistivity},
author = {Mills, Edmund M. and Kleine-Boymann, Matthias and Janek, Juergen and Yang, Hao and Browning, Nigel D. and Takamura, Yayoi and Kim, Sangtae},
abstractNote = {In recent years, interface engineering of solid electrolytes has been explored to increase their ionic conductivity and improve the performance of solid oxide fuel cells and other electrochemical power sources. It has been observed that the ionic conductivity of epitaxially grown thin films of some electrolytes is dramatically enhanced, which is often attributed to effects (e.g. strain-induced mobility changes) at the heterophase boundary with the substrate. Still largely unexplored is the possibility of manipulation of grain boundary resistivity in polycrystalline solid electrolyte films, clearly a limiting factor in their ionic conductivity. Here in this paper, we report that the ionic conductivity of yttria stabilized zirconia thin films with nano-columnar grains grown on a MgO substrate nearly reaches that of the corresponding single crystal when the thickness of the films becomes less than roughly 8 nm (smaller by a factor of three at 500 °C). Using impedance spectroscopy, the grain boundary resistivity was probed as a function of film thickness. The resistivity of the grain boundaries near the film–substrate interface and film surface (within 4 nm of each) was almost entirely eliminated. This minimization of grain boundary resistivity is attributed to Mg2+ diffusion from the MgO substrate into the YSZ grain boundaries, which is supported by time of flight secondary ion mass spectroscopy measurements. We suggest grain boundary “design” as an attractive method to obtain highly conductive solid electrolyte thin films.},
doi = {10.1039/c5cp08032k},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 15,
volume = 18,
place = {United States},
year = {2016},
month = {3}
}

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Cited by: 12 works
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Works referenced in this record:

Grain Boundary Blocking Effect in Zirconia: A Schottky Barrier Analysis
journal, January 2001

  • Guo, X.; Maier, J.
  • Journal of The Electrochemical Society, Vol. 148, Issue 3
  • DOI: 10.1149/1.1348267

Colossal Ionic Conductivity at Interfaces of Epitaxial ZrO2:Y2O3/SrTiO3 Heterostructures
journal, August 2008

  • Garcia-Barriocanal, J.; Rivera-Calzada, A.; Varela, M.
  • Science, Vol. 321, Issue 5889
  • DOI: 10.1126/science.1156393

Microstructures of CGO and YSZ Thin Films by Pulsed Laser Deposition
journal, December 2007

  • Infortuna, A.; Harvey, A. S.; Gauckler, L. J.
  • Advanced Functional Materials, Vol. 18, Issue 1
  • DOI: 10.1002/adfm.200700136

Columnar grain boundary coherence in yttria-stabilized zirconia thin film: effects on ionic conductivity
journal, January 2014

  • Kiguchi, Takanori; Konno, Toyohiko J.; Funakubo, Hiroshi
  • Journal of the Ceramic Society of Japan, Vol. 122, Issue 1421
  • DOI: 10.2109/jcersj2.122.72

Lowering the Temperature of Solid Oxide Fuel Cells
journal, November 2011


Ceria-based nanocomposite with simultaneous proton and oxygen ion conductivity for low-temperature solid oxide fuel cells
journal, March 2011


Solid oxide fuel cell (SOFC) technical challenges and solutions from nano-aspects
journal, October 2009

  • Zhu, Bin
  • International Journal of Energy Research, Vol. 33, Issue 13
  • DOI: 10.1002/er.1600

Nanoscale effects on the ionic conductivity in highly textured YSZ thin films
journal, April 2005


Oxygen tracer diffusion along interfaces of strained Y 2 O 3 /YSZ multilayers
journal, January 2013

  • Aydin, Halit; Korte, Carsten; Rohnke, Marcus
  • Phys. Chem. Chem. Phys., Vol. 15, Issue 6
  • DOI: 10.1039/C2CP43231E

Electrical properties of the grain boundaries of oxygen ion conductors: Acceptor-doped zirconia and ceria
journal, February 2006


Influence of interface structure on mass transport in phase boundaries between different ionic materials: Experimental studies and formal considerations
journal, March 2009

  • Korte, Carsten; Schichtel, N.; Hesse, D.
  • Monatshefte für Chemie - Chemical Monthly, Vol. 140, Issue 9
  • DOI: 10.1007/s00706-009-0125-7

Grain Boundary Diffusion of Magnesium in Zirconia
journal, September 2002


Low-Temperature Superionic Conductivity in Strained Yttria-Stabilized Zirconia
journal, May 2010

  • Sillassen, Michael; Eklund, Per; Pryds, Nini
  • Advanced Functional Materials, Vol. 20, Issue 13
  • DOI: 10.1002/adfm.201000071

A theoretical model for composite electrolytes—I. Space charge layer as a cause for charge-carrier enhancement
journal, August 1995


On the variability of reported ionic conductivity in nanoscale YSZ thin films
journal, September 2013


Heterogeneously doped nanocrystalline ceria films by grain boundary diffusion: Impact on transport properties
journal, March 2008

  • Litzelman, Scott J.; De Souza, Roger A.; Butz, Benjamin
  • Journal of Electroceramics, Vol. 22, Issue 4
  • DOI: 10.1007/s10832-008-9445-y

Numerical Study of Grain Boundary Diffusion in Nanocrystalline Materials
journal, April 2005


Ionic conductivity in oxide heterostructures: the role of interfaces
journal, October 2010

  • Fabbri, Emiliana; Pergolesi, Daniele; Traversa, Enrico
  • Science and Technology of Advanced Materials, Vol. 11, Issue 5
  • DOI: 10.1088/1468-6996/11/5/054503