Unusual aliovalent doping effects on oxygen non-stoichiometry in medium-entropy compositionally complex perovskite oxides

Zhang, Dawei; Park, Jiyun; Xu, Boyuan; Liu, Cijie; Li, Wei; Liu, Xingbo; Qi, Yue; Luo, Jian

doi:10.1039/d2dt03759a

Title: Unusual aliovalent doping effects on oxygen non-stoichiometry in medium-entropy compositionally complex perovskite oxides

Journal Article · Tue Dec 20 00:00:00 EST 2022 · Dalton Transactions

DOI:https://doi.org/10.1039/d2dt03759a· OSTI ID:2203859

Zhang, Dawei ^[1]; Park, Jiyun ^[2];

^[2]; Liu, Cijie ^[3];

^[3];

^[3]; Qi, Yue ^[2];

^[1]

University of California San Diego, La Jolla, CA (United States)
Brown University, Providence, RI (United States)
West Virginia University, Morgantown, WV (United States)

Aliovalent doping of perovskite oxides can tune the oxygen vacancy formation energy. This work discovers normal vs. abnormal aliovalent doping effects on redox behaviors in medium-entropy compositionally complex perovskite oxides (CCPOs) (La_1–xSr_x)(Mn_1/3Fe_1/3Ti_1/3)O_3–δ (LS_MFT) vs. (La_1–xSr_x)(Mn_1/3Fe_1/3Cr_1/3)O_3–δ (LS_MFC). In the LS_MFC series, the oxygen non-stoichiometry range Δδ (= δ_red – δ_ox) linearly depends on the Sr molar ratio x, while the LS_MFT series shows a V-shape dependence of Δδ on x. This unusual observation is investigated and explained based on the analysis of the energy loss near edge structure (ELNES) in STEM electron energy loss spectroscopy, along with density functional theory (DFT) calculations. In LS_MFC, Cr–L_2,3, Mn–L_2,3 and Fe–L_2,3 peaks have a similar linear shift to higher energy with increasing x, which indicates higher oxidation states of Cr, Mn, and Fe with lower oxygen vacancy formation energies. In LS_MFT, the V-shape of the Δδ vs. x curve is caused by the stable Ti⁴⁺ state and a V-shape Mn/Fe valency dependence on x. Furthermore, this study suggests the possible existence of different (including unexpected) coupled aliovalent doping effects in CCPOs with multiple B-site redox active elements.

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Research Organization:: University of California San Diego, La Jolla, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO); USDOE

Grant/Contract Number:: EE0008839

OSTI ID:: 2203859

Alternate ID(s):: OSTI ID: 1907912

Journal Information:: Dalton Transactions, Vol. 52, Issue 4; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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