Oxygen release from BaLnMn2O6 (Ln: Pr, Nd, Y) under reducing conditions as studied by neutron diffraction

Klimkowicz, Alicja; Świerczek, Konrad; Zheng, Kun; Wallacher, Dirk; Takasaki, Akito

doi:10.1007/s10853-017-0883-2

Cited by 13 publications

(10 citation statements)

References 28 publications

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“…This is in good agreement with behavior of YBaMn 2 O 5+δ , for which YBaMn 2 O 5.5 phase is well-known. 34,41 The observed slowdown of the reduction, which starts as the oxygen content is approaching 5 was also observed for REBaMn 2 O 5+δ .…”

Section: Methodssupporting

confidence: 57%

“…However, in recent years their oxygen storage-related ability became also of interest . It has been documented in practical experiments that fully reversible oxygen content change, from the reduced REBaMn 2 O 5 to the oxidized REBaMn 2 O 6 (change of the oxygen content close to 1 mol per mole of the material) can be induced in the so-called oxygen partial pressure ( p O 2 ) swing process . Working principle for such the oxygen storage materials (OSM) depends on the redox process of manganese (e.g., REBaMn 2 2.5+ O 5 –REBaMn 2 3.5+ O 6 ), and takes place at elevated temperatures (ca.…”

Section: Introductionmentioning

confidence: 99%

“…3.7 wt %. Simultaneously, the oxygen uptake/release characteristics are fast and fully reversible at or below 500 °C. , It should be emphasized that such the extraordinary oxygen storage properties of REBaMn 2 O 5+δ materials result also from their layered crystal structure, as during the intake/release processes, oxygen anions occupying RE-related layer are the ones being inserted/extracted into/from the material. This process can occur relatively easily (and therefore with fast kinetics), due to the mentioned lowered strength of the oxygen bonds at those sites.…”

Section: Introductionmentioning

confidence: 99%

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Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

et al. 2018

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Belonging to the not fully explored REBaCo2‑x Mn x O5+δ system, a series of REBaCoMnO5+δ (RE: selected rare earth elements) oxides having perovskite-type structure is synthesized and studied in terms of their structural properties, oxygen content, stability, thermal expansion, and transport properties. Impact of RE3+ on physicochemical properties of the compounds is derived, with smaller cations causing a decrease of the unit cell volume, lowering of the total oxygen content and thermal expansion, but also suppressing electrical conductivity. It is shown that a proper chemical modification enables to successfully utilize REBaCoMnO5+δ in applications, in which redox processes associated with oxygen reduction/oxidation and transport determine the effectiveness of the working material. In particular, NdBaCoMnO5+δ (with larger Nd3+) shows good chemical stability in relation to Ce0.8Gd0.2O2−δ and La0.8Sr0.2Ga0.8Mg0.2O3‑δ solid electrolytes and moderate thermal expansion, 20.04(4)·10–6 K–1 in 300–900 °C. In symmetrical configuration with La0.8Sr0.2Ga0.8Mg0.2O3‑δ electrolyte its cathodic polarization resistance is found to be only 0.036 Ω cm2 at 900 °C, making it an excellent candidate cathode for solid oxide fuel cells. At the same time, YBaCoMnO5+δ (with small and cheap Y3+) delivers reversible oxygen storage capacity surpassing 3.4 wt % during the oxygen partial pressure swing process between air and 5 vol % H2 in Ar at 500 °C.

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Section: Methodssupporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

et al. 2018

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“…This can be considered as surprising, since perovskite or similarly-structured oxide samples obtained by quenching and/or annealing at different temperatures and p O2 showed much stronger variations of the crystal structure. Moreover, relatively strong (and monotonic) dependence between the unit cell dimensions and the oxygen content is known to be present [33][34][35]. While it was expected that the increase in the electrochemical oxidation oxygen concentration should cause a noticeable decrease of the unit cell volume of the compounds, this did not happen.…”

Section: Crystal Structurementioning

confidence: 99%

Peculiar Properties of Electrochemically Oxidized SmBaCo2−xMnxO5+δ (x = 0; 0.5 and 1) A-Site Ordered Perovskites

2020

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Fully-stoichiometric SmBaCo2-xMnxO6 oxides (x = 0, 0.5, 1) were obtained through the electrochemical oxidation method performed in 1 M KOH solution from starting materials having close to equilibrium oxygen content. Cycling voltammetry scans allow us to recognize the voltage range (0.3–0.55 V vs. Hg/HgO electrode) for which electrochemical oxidation occurs with high efficiency. In a similarly performed galvanostatic experiment, the value of the stabilized voltage recorded during the oxidation increased with higher Mn content, which seems to relate to the electronic structure of the compounds. Results of the iodometric titration and thermogravimetric analysis prove that the proposed technique allows for an increase in the oxygen content in SmBaCo2-xMnxO5+δ materials to values close to 6 (δ ≈ 1). While the expected significant enhancement of the total conductivity was observed for the oxidized samples, surprisingly, their crystal structure only underwent slight modification. This can be interpreted as due to the unique nature of the oxygen intercalation process at room temperature.

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“…Furthermore, PBMO has proven to be very stable over a wide range of temperatures and oxygen partial pressures [21]. In this sense, PBMO has shown almost complete reversibility between the fully-reduced (δ~0) and fully-oxidized (δ~1) phases at relatively low temperatures (200-500 • C) when the oxygen partial pressure is alternated between reducing and oxidizing conditions [21,22]. Moreover, it has also been proven to withstand redox cycles at higher temperatures (up to 950 • C) with only a small decrease in the maximum oxygen storage capacity [23].…”

Section: Introductionmentioning

confidence: 99%

A Novel, Simple and Highly Efficient Route to Obtain PrBaMn2O5+δ Double Perovskite: Mechanochemical Synthesis

2021

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In this work, a mechanochemical route was proposed for the synthesis of the PrBaMn2O5+δ (PMBO) double layered perovskite phase. The mechanochemical reaction between Pr6O11, BaO2, and MnO powders with cationic stoichiometric ratios of 1/1/2 for Pr/Ba/Mn was performed using high-energy milling conditions in air. After 150 min of milling, a new phase with perovskite structure and cubic symmetry consistent with the A-site disordered Pr0.5Ba0.5MnO3 phase was formed. When this new phase was subsequently annealed at a high temperature in an inert Ar atmosphere, the layered PrBaMn2O5+δ phase was obtained without needing to use a reducing atmosphere. At 1100 °C, the fully reduced layered PrBaMn2O5 phase was achieved. A weight gain was observed in the 200–300 °C temperature range when this fully reduced phase was annealed in air, which was consistent with the transformation into the fully oxidized PrBaMn2O6 phase. The microstructural characterization by SEM, TEM, and HRTEM ascertained the formation of the intended PrBaMn2O5+δ phase. Electrical characterization shows very high electrical conductivity of layered PBMO in a reducing atmosphere and suitable in an oxidizing atmosphere, becoming, therefore, excellent candidates as solid oxide fuel cell (SOFC electrodes).

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Oxygen release from BaLnMn2O6 (Ln: Pr, Nd, Y) under reducing conditions as studied by neutron diffraction

Cited by 13 publications

References 28 publications

Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Peculiar Properties of Electrochemically Oxidized SmBaCo2−xMnxO5+δ (x = 0; 0.5 and 1) A-Site Ordered Perovskites

A Novel, Simple and Highly Efficient Route to Obtain PrBaMn2O5+δ Double Perovskite: Mechanochemical Synthesis

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Oxygen release from BaLnMn2O6 (Ln: Pr, Nd, Y) under reducing conditions as studied by neutron diffraction

Cited by 13 publications

References 28 publications

Versatile Application of Redox Processes for REBaCoMnO5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Versatile Application of Redox Processes for REBaCoMnO5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Peculiar Properties of Electrochemically Oxidized SmBaCo2−xMnxO5+δ (x = 0; 0.5 and 1) A-Site Ordered Perovskites

A Novel, Simple and Highly Efficient Route to Obtain PrBaMn2O5+δ Double Perovskite: Mechanochemical Synthesis

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Product

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Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides

Versatile Application of Redox Processes for REBaCoMnO_5+δ (RE: La, Pr, Nd, Sm, Gd, and Y) Oxides