Strain-Dependent Surface Defect Equilibria of Mixed Ionic-Electronic Conducting Perovskites

Wang, Jiayue; Yang, Jing; Opitz, Alexander Karl; Kalaev, Dmitri; Nenning, Andreas; Crumlin, Ethan J.; Sadowski, Jerzy T.; Waluyo, Iradwikanari; Hunt, Adrian; Tuller, Harry L.; Yildiz, Bilge

doi:10.1021/acs.chemmater.2c00614

Title: Strain-Dependent Surface Defect Equilibria of Mixed Ionic-Electronic Conducting Perovskites

Journal Article · 31 May 2022 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.2c00614 · OSTI ID:1871819

^[1];

^[2]; Kalaev, Dmitri ^[1]; Nenning, Andreas ^[2];

^[3];

^[4];

^[5];

^[5]; Tuller, Harry L. ^[1];

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Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Technische Univ. Wien (Austria)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source

We report understanding the surface defect chemistry and its strain dependency is essential in developing next-generation electrochemical devices. However, due to their nanoscale dimensions, surface defects cannot be accessed by conventional techniques used in bulk defect studies. Here, we constructed the strain-dependent surface defect equilibria (i.e., the Brouwer diagram) of mixed ionic-electronic conducting perovskite oxides with near ambient pressure X-ray absorption spectroscopy. Using coherently strained thin-film La_0.6Sr_0.4Fe_O3 (LSF) as model systems, we probed their surface defect equilibria at 400 °C in oxygen partial pressures between 1 to 10_-5 Torr. We found that the electron holes on the LSF surfaces have strong oxygen character, regardless of the strain states. Nevertheless, tensile strain makes the LSF surface more reducible than the compressed counterpart. These two observations were then validated using first-principles calculations. Finally, with the aid of thermodynamic analyses, we showed that the strain-dependent surface defect equilibria of LSF can be captured by bulk-like ideal solution defect models with shifted oxygen chemical potentials. The findings and methodology presented in this study enable quantitative determination of the surface defect chemistry, which is crucial to understanding and designing functional surfaces for efficient conversions of energy and fuels.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Exelon Corporation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0012704

OSTI ID:: 1871819

Report Number(s):: BNL-223062-2022-JAAM; BNL-223840-2023-JAAM

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 11 Vol. 34; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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perovskites
strain
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Title: Strain-Dependent Surface Defect Equilibria of Mixed Ionic-Electronic Conducting Perovskites

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