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Probing the reaction pathway in (La_(0.8)Sr_(0.2))_(0.95)MnO_(3+δ) using libraries of thin film microelectrodes

Usiskin, Robert E. and Maruyama, Shingo and Kucharczyk, Chris J. and Takeuchi, Ichiro and Haile, Sossina M. (2015) Probing the reaction pathway in (La_(0.8)Sr_(0.2))_(0.95)MnO_(3+δ) using libraries of thin film microelectrodes. Journal of Materials Chemistry A, 3 (38). pp. 19330-19345. ISSN 2050-7488. doi:10.1039/C5TA02428E.

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Libraries of (La_(0.8)Sr_(0.2))_(0.95)MnO_(3+δ) (LSM) thin film microelectrodes with systematically varied thickness or growth temperature were prepared by pulsed laser deposition, and a novel robotic instrument was used to characterize these libraries in automated fashion by impedance spectroscopy. The measured impedance spectra are found to be described well by an electrochemical model based on a generalized transmission model for a mixed conducting oxide, and all trends are consistent with a reaction pathway involving oxygen reduction over the LSM surface followed by diffusion through the film and into the electrolyte substrate. The surface activity is found to be correlated with the number of exposed grain boundary sites, which decreases with either increasing film thickness (at constant growth temperature) or increasing film growth temperature (at constant thickness). These findings suggest that exposed grain boundaries in LSM films are more active than exposed grains towards the rate-limiting surface process, and that oxygen ion diffusion through polycrystalline LSM films is faster than many prior studies have concluded.

Item Type:Article
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URLURL TypeDescription Information
Kucharczyk, Chris J.0000-0002-4712-839X
Haile, Sossina M.0000-0002-5293-6252
Alternate Title:Probing the Reaction Pathway in (La0.8Sr0.2)0.95MnO3+δ Using Libraries of Thin Film
Additional Information:© Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Received 03 Apr 2015, Accepted 02 Aug 2015, First published online 27 Aug 2015. The authors would like to thank McAllister Technical Services for their help in designing and assembling the automated impedance microprobe, and Ben Meyers and Xinqi Chen at University for their assistance in performing the FIB-SEM and SIMS characterization, respectively. This work was funded by the National Science Foundation via awards DMR-0520565 and EFRI-1038307, the Resnick Sustainability Institute at the California Institute of Technology, the National Central University of Taiwan, and the W. M. Keck Foundation. Selected facilities used were supported by the National Science Foundation via Northwestern University's MRSEC, DMR-1121262.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Resnick Sustainability InstituteUNSPECIFIED
National Central University, TaiwanUNSPECIFIED
W. M. Keck FoundationUNSPECIFIED
Issue or Number:38
Record Number:CaltechAUTHORS:20150828-120355577
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59958
Deposited By: Joy Painter
Deposited On:28 Aug 2015 19:49
Last Modified:10 Nov 2021 22:27

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