Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr1−xLnx)2NiO4 (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study

Zhang, Yanxing; Wang, Wei; Wang, Yudong; Xu, Nengneng; Tian, Guang; Karsili, Tolga N. V.; Yang, Jinbo; Zhou, Xiao Dong

doi:10.1149/1945-7111/ac4057

Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr_1−xLn_x)₂NiO₄ (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study

Journal Article · Thu Dec 16 00:00:00 EST 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac4057· OSTI ID:1980863

^[1]; Wang, Wei ^[2]; ^[3]; Xu, Nengneng ^[3]; Tian, Guang ^[4]; Karsili, Tolga N. V. ^[3]; Yang, Jinbo ^[4]; ^[3]

Henan Normal University (China); University of Louisiana at Lafayette, LA (United States); OSTI
Henan Normal University (China)
University of Louisiana at Lafayette, LA (United States)
Peking University, Beijing (China)

Praseodymium nickelate, Pr₂NiO₄ (PNO), is a promising electrode to promote oxygen reduction reaction (ORR) in a solid oxide fuel cell, but it exhibits phase transformation during electrochemical operation. The origin of the simultaneous phase transformation and high electrochemical performance remains obscure. We carried out a systematic density functional theory study to elucidate the mechanism for this conjugated phenomenon. Charge, electronic structure, and normal-mode analysis suggest the presence of peroxide. Our study shows that the formation of peroxide (O₂^2–) is attributed to both oxygen interstitials and Pr vacancies. The peroxide species limits the oxygen ion migration due to the additional energy required to break its O–O bond, which leads to a decrease in ORR activity. Subsequently, we investigate the diffusion paths of Pr-ions while comparing them with those of other Ln³⁺ ions (La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) in PNO. The formation energies for various Ln³⁺ cation occupancies are calculated, as well as segregation energies in CeO₂(111) surfaces. Lastly, criteria for effective Ln³⁺ dopants are developed. La, Nd, and Pm are proposed as potential substituents in PNO to obtain a stable structure.

View Accepted Manuscript (DOE)

Research Organization:: University of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: FE0026097

OSTI ID:: 1980863

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 12 Vol. 168; ISSN 0013-4651

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

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Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr1−xLnx)2NiO4 (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study

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Role of Pr-Vacancies and O-Interstitials on the Activity and Stability of (Pr_1−xLn_x)₂NiO₄ (Ln = La, Nd, Pm, Sm, Gd, Tb, Dy, and Ho) towards Oxygen Reduction Reactions: A DFT Study