Optimizing proton conductivity in zirconates through defect engineering

Rowberg, Andrew J. E.; Weston, Leigh; Van de Walle, Chris G.

doi:10.1021/acsaem.8b02222

Optimizing proton conductivity in zirconates through defect engineering

Journal Article · Tue Mar 12 00:00:00 EDT 2019 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.8b02222· OSTI ID:1499049

^[1]; Weston, Leigh ^[2]; ^[3]

Univ. of California, Santa Barbara, CA (United States). Materials Dept.; Materials Department, University of California, Santa Barbara
Univ. of California, Santa Barbara, CA (United States). Materials Dept.; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Energy Technologies Area
Univ. of California, Santa Barbara, CA (United States). Materials Dept.

The alkaline-earth zirconates (CaZrO₃, SrZrO₃, and BaZrO₃) are under active investigation as solid-state electrolytes in hydrogen fuel cells. Their performance as proton conductors depends critically on the properties of acceptor dopants. Here, we use first-principles calculations to study the role of acceptors and point defects in incorporating protons through an oxygen-vacancy-mediated process. For CaZrO₃, we find that Zr_Ca antisites suppress formation of oxygen vacancies. Other intrinsic point defects are shown not to hinder performance. Common unintentional impurities, such as C and N, are not good acceptors but can incorporate in other configurations. Our results show that the effectiveness of common dopants such as Sc and Y is limited by self-compensation due to their incorporation on the "wrong" cation site, where they act as donors. We demonstrate that using alkali metal dopants overcomes this problem, as the formation energy of compensating donors is very high. Alkali metal dopants also have low binding energies for protons, reducing their tendency to act as traps and hence enhancing proton conductivity. As a result, our guidelines for choosing acceptor dopants and optimizing synthesis conditions can greatly improve the efficacy of these proton-conducting oxides as solid-state electrolytes.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of California, Santa Barbara, CA (United States); Univ. of California, Santa Barbara, CA (United States). Materials Dept.

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

Grant/Contract Number:: AC02-05CH11231; FG02-07ER46434

OSTI ID:: 1499049

Alternate ID(s):: OSTI ID: 1736255

Journal Information:: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 4 Vol. 2; ISSN 2574-0962

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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08 HYDROGEN
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acceptor doping
binding energy
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density functional theory
first-principles calculations
hydrogen
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ionic conductivity
proton conductivity
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Optimizing proton conductivity in zirconates through defect engineering

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References (47)

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