Long-range oxygen ordering linked to topotactic oxygen release in Pr<sub>2</sub>NiO<sub>4+δ</sub> fuel cell cathode material

Dutta, Rajesh; Maity, Avishek; Marsicano, Anna; Ceretti, Monica; Chernyshov, Dmitry; Bosak, Alexeï; Villesuzanne, Antoine; Roth, Georg; Perversi, Giuditta; Paulus, Werner

doi:10.1039/d0ta04652c

Cited by 13 publications

(28 citation statements)

References 41 publications

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“…In addition, structural Bragg peaks from epitaxially intergrown NiO as reported in Ref. [25] were also observed at all the investigated temperatures. An example of the manually indexed experimental and idealized (hk0) plane is presented in Figs.…”

Section: Excess Oxygen Ordering and The Additional Magnetic Phasesupporting

confidence: 75%

“…Stronger correlations among the excess oxygen atoms appear with increasing excess oxygen doping concentration δ. Consequently, a three-dimensional (3D) ordering pattern of excess oxygen atoms is evidenced at δ 0.125 [24]. Very recently, a complex 3D ordering of excess oxygen atoms has been reported for homologous Pr 2 NiO 4+δ with δ 0.22-0.25, i.e., with a δ value close to the most nonstoichiometric limit, revealing translational periodicities of almost 100 Å [25]. The ordered arrangement of excess oxygen atoms leads to an ordered deformation of NiO 2 planes, which provides a modulated potential that can pin the charge stripes to the lattice.…”

Section: Introductionmentioning

confidence: 97%

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Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Maity

Ceretti

Keller

et al. 2021

Phys. Rev. Materials

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Hole doping in Nd 2 NiO 4.00 can be achieved either by substituting the trivalent Nd atoms by bivalent alkalineearth metals or by oxygen doping, yielding Nd 2 NiO 4+δ . While the alkaline-earth-metal atoms are statistically distributed on the rare-earth sites, the extra oxygen atoms in the interstitial lattice remain mobile down to ambient temperature and allow complex ordering scenarios depending on δ and T . Thereby the oxygen ordering, usually setting in far above room temperature, adds an additional degree of freedom on top of charge, spin, and orbital ordering, which appear at much lower temperatures. In this study, we investigated the interplay between oxygen and spin ordering for a low oxygen doping concentration, i.e., Nd 2 NiO 4.10 . Although the extra oxygen doping level remains rather modest with only 1 out of 20 possible interstitial tetrahedral lattice sites occupied, we observed by single-crystal neutron diffraction the presence of a complex three-dimensional (3D) modulated structure related to oxygen ordering already at ambient, the modulation vectors being ±2/13a*±3/13b*, ±3/13b*±2/13b*, and ±1/5a*±1/2c*, and satellite reflections up to fourth order. Temperature-dependent neutron-diffraction studies indicate the coexistence of oxygen and magnetic ordering below T N 48 K, the wave vector of the Ni sublattice being k = (100). In addition, magnetic satellite reflections adapt exactly the same modulation vectors as found for the oxygen ordering, evidencing a unique coexistence of 3D modulated ordering for spin and oxygen ordering in Nd 2 NiO 4.10 . Temperature-dependent measurements of magnetic intensities suggest two magnetic phase transitions below 48 and 20 K, indicating two distinct onsets of magnetic ordering for the Ni and Nd sublattices, respectively.

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Section: Excess Oxygen Ordering and The Additional Magnetic Phasesupporting

confidence: 75%

Section: Introductionmentioning

confidence: 97%

Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Maity

Ceretti

Keller

et al. 2021

Phys. Rev. Materials

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“…As reported previously, the single-crystal structure of PNO is rather complex (Ceretti et al, 2015;Dutta et al, 2020), with up to 16 monoclinic twin individuals by pseudomerohedry. At 900 C, twinning is no longer an issue as for data collections both in O 2 atmosphere and in secondary vacuum the symmetry was found to be tetragonal.…”

Section: Diffraction Measurements On Oxygen Stoichiometry Controlled Pr 2 Nio 4+d Single Crystalssupporting

confidence: 74%

“…Oxygen electrochemical intercalation into stoichiometric Pr 2 NiO 4.00 yields then the formation of a non-stoichiometric tetragonal phase with 0.08 < < 0.13 (space group P4 2 /ncm), while for higher interstitial oxygen concentrations ( = 0.18-0.25) the symmetry lowers again to orthorhombic or monoclinic, showing complex oxygen ordering adapting a modulated structure (Dutta et al, 2020). Upon heating in air, PNO ( ' 0.23) undergoes a monoclinic/tetragonal phase transition at around 365 C (space group F4/mmm), while the oxygen stoichiometry slightly increases towards ' 0.25.…”

Section: Diffraction Measurements On Oxygen Stoichiometry Controlled Pr 2 Nio 4+d Single Crystalsmentioning

confidence: 99%

Infrared furnace for in situ neutron single-crystal diffraction studies in controlled gas atmospheres at high temperatures

Magro¹,

Ceretti²,

Meven³

et al. 2021

J Appl Cryst

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To understand oxygen diffusion mechanisms in non-stoichiometric oxides, the possibility to explore structural changes as a function of the oxygen partial pressure with temperature and related oxygen bulk stoichiometry is mandatory. This article reports on the realization of a high-temperature furnace, suitable for single-crystal neutron diffraction, working continuously at temperatures of up to 1000°C at different and adjustable partial gas pressures of up to 2 bar (1 bar = 100 kPa). This allows exploration of the phase diagrams of non-stoichiometric oxides under in situ conditions and controlled oxygen partial pressure. As a pilot study, the structural changes of Pr2NiO4+δ were explored at room temperature (δ ≃ 0.24) and at 900°C under 1 bar P(O2) (δ ≃ 0.13) as well as under secondary vacuum (approximately 10−5 mbar) conditions yielding a δ close to zero. The strong anharmonic displacements of the apical oxygen atoms along the [110] shallow diffusion pathway, which were previously observed at room temperature and 400°C, become more isotropic at 900°C. The study shows that the anisotropic oxygen displacements, here related to lattice instabilities, play a major role in understanding oxygen diffusion pathways and related activation energies at moderate temperatures. This also shows the importance of the availability of reaction cells for single-crystal neutron diffraction to explore the phase diagram and associated structural changes of non-stoichiometric oxygen ion conductors and respective diffusion mechanisms.

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“…Fuel cells, including anode, cathode and electrolyte, convert chemical energy (such as hydrogen and methanol) to electrical energy through electrochemical reaction between positively charged protons and oxidizers (air or pure oxygen)., [89] and are regarded as pollution-free power source with higher energy efficiency and density compared with other conventional energy conversion systems. [90] At present, the fuel cells technology cannot meet the demand of mass promotion considering its high cost-precious metal on anode side, and relatively poor durability-slow oxygen reduction reaction on cathode side.…”

Section: Othersmentioning

confidence: 99%

Optimization Design and Application of Niobium‐Based Materials in Electrochemical Energy Storage

Lian

Yang

Wang

et al. 2020

Adv Energy and Sustain Res

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In various energy storage devices, the development and research of electrode materials has always been a key factor. Nb‐based materials are one choice of energy storage materials because of the good ion‐diffusion channels and high theoretical capacity. More importantly, their advantages, such as safe potential range, high structural stability, and highly reversible redox reaction with small strain, are conducive to efficient, safe, and stable energy storage development. Based on aforementioned superiority, much of the research is to further optimize performance of Nb‐based materials by unique nano‐morphology design, lattice regulation, and functional additives composition, showing good electrochemical performance in many kinds of devices. This review mainly introduces the classification of Nb‐based materials used for energy storage, their application in different battery systems, and common optimization methods. Accordingly, the deficiencies and prospects of Nb‐based materials are also discussed in detail.

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Long-range oxygen ordering linked to topotactic oxygen release in Pr₂NiO_4+δ fuel cell cathode material

Abstract:
Complex oxygen ordering evidenced for the oxygen membrane cathode material Pr₂NiO_4.25 at room temperature with translational periodicities attaining almost 100 Å by single-crystal synchrotron diffraction studies.

Cited by 13 publications

References 41 publications

Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Infrared furnace for in situ neutron single-crystal diffraction studies in controlled gas atmospheres at high temperatures

Optimization Design and Application of Niobium‐Based Materials in Electrochemical Energy Storage

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Long-range oxygen ordering linked to topotactic oxygen release in Pr2NiO4+δ fuel cell cathode material

Abstract: Complex oxygen ordering evidenced for the oxygen membrane cathode material Pr2NiO4.25 at room temperature with translational periodicities attaining almost 100 Å by single-crystal synchrotron diffraction studies.

Cited by 13 publications

References 41 publications

Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Interdependent scaling of long-range oxygen and magnetic ordering in nonstoichiometric Nd2NiO4.10

Infrared furnace for in situ neutron single-crystal diffraction studies in controlled gas atmospheres at high temperatures

Optimization Design and Application of Niobium‐Based Materials in Electrochemical Energy Storage

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Product

Resources

About

Long-range oxygen ordering linked to topotactic oxygen release in Pr₂NiO_4+δ fuel cell cathode material

Abstract:
Complex oxygen ordering evidenced for the oxygen membrane cathode material Pr₂NiO_4.25 at room temperature with translational periodicities attaining almost 100 Å by single-crystal synchrotron diffraction studies.