Journal Article

FZJ-2019-00342

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png (Nd/Pr) 2 NiO 4+δ : Reaction Intermediates and Redox Behavior Explored by in Situ Neutron Powder Diffraction during Electrochemical Oxygen Intercalation

Ceretti, M. (Corresponding author) ; Wahyudi, O. ; André, G. ; Meven, M.MLZ*FZJ*RWTH* ; Villesuzanne, A. ; Paulus, W.

2018
American Chemical Society Washington, DC

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Please use a persistent id in citations: doi:10.1021/acs.inorgchem.8b00393

Abstract: Oxygen intercalation/deintercalation in Pr2NiO4+δ and Nd2NiO4+δ was followed by in situ by neutron powder diffraction during the electrochemical oxidation/reduction reaction, in a dedicated reaction cell at room temperature. Three phases were identified for both systems: orthorhombic RE2NiO4.23, obtained by classical solid-state reaction, gets reduced in a 2-phase reaction step to a tetragonal intermediate phase RE2NiO4+δ with 0.07 ≤ δ ≤ 0.10, which again transforms on further reduction in a 2-phase reaction step towards the stoichiometric RE2NiO4.0. Electrochemical oxidation does not proceed fully reversibly for both cases: while the re-oxidation of Nd2NiO4+δ is limited to the tetragonal intermediate phase with δ = 0.10, the homologous Pr2NiO4+δ can be re-oxidized up to δ = 0.17, showing orthorhombic symmetry. For the tetragonal Pr2NiO4.12 phase, we were able to establish a complex anharmonic displacement behavior as analyzed by single crystal neutron diffraction and Maximum Entropy Analysis, in agreement with a low-T diffusion pathway for oxygen ions activated by lattice dynamics.

Keyword(s): Energy (1st) ; Crystallography (2nd) ; Chemistry (2nd)

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Contributing Institute(s):

1. JCNS-FRM-II (JCNS-FRM-II)
2. Streumethoden (JCNS-2)
3. Heinz Maier-Leibnitz Zentrum (MLZ)

Research Program(s):

1. 6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623) (POF3-623)
2. 6G15 - FRM II / MLZ (POF3-6G15) (POF3-6G15)

Experiment(s):

1. HEiDi: Single crystal diffractometer on hot source (SR9b)
2. Measurement at external facility

Appears in the scientific report 2018

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Database coverage:
; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; Ebsco Academic Search ; IF < 5 ; JCR ; NCBI Molecular Biology Database ; Nationallizenz ; SCOPUS ; Science Citation Index ; Science Citation Index Expanded ; Web of Science Core Collection

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