Oxygen Storage Property and Chemical Stability of SrFe1–xTixO3−δ with Robust Perovskite Structure

Demizu, Akito; Beppu, Kosuke; Hosokawa, Saburo; Kato, Kazúo; Asakura, Hiroyuki; Teramura, Kentaro; Tanaka, Tsunehiro

doi:10.1021/acs.jpcc.7b06078

Cited by 29 publications

(42 citation statements)

References 38 publications

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“…Perovskites (ABO 3 ) and perovskite-like oxides have been studied as OSMs because of their stability as well as high oxygen deficiency or oxygen excess. In particular, perovskites, whose B sites are occupied by elements with easily changed valence, such as Mn, − Fe, − and Co ,, have been studied widely. OSMs used for oxygen separation by the PSA process need to be able to release stored oxygen in the presence of ambient oxygen rather than in a reducing atmosphere, in addition to having large oxygen storage capacity.…”

Section: Introductionmentioning

confidence: 99%

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Tanahashi

Omura

Naya

et al. 2021

ACS Sustainable Chem. Eng.

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Pressure swing adsorption (PSA) is expected to replace the currently used energy-intensive cryogenic distillation process for oxygen separation. For realizing an energy-saving PSA, an oxygen storage material (OSM) with a high oxygen storage capacity and narrow pressure swing gap during reversible oxygen storage and release is necessary. While Ca 2 AlMnO 5 is a promising candidate for PSA, it exhibits a large pressure hysteresis loop during oxygen storage and release. In this study, we investigated the effect of Sr doping of the Ca sites of Ca 2 AlMnO 5 (Ca 2−x Sr x AlMnO 5 ) on the phase compositions and oxygen storage/release performance with the aim of realizing an optimum OSM for the PSA process. From the results of structural refinement, while the oxygen release phase has a Brownmillerite (BM) structure (n = 1) at 0 ≤ x ≤ 1.0, BM (n = 3) and oxygen-defective perovskite were found to be the main structures in the oxygen storage phase at 0 ≤ x < 0.50 and 0.50 ≤ x ≤ 1.0, respectively. The oxygen storage/release temperature obtained from the thermogravimetry curves decreased in the 0 ≤ x < 0.50 range and increased in the 0.50 ≤ x ≤ 1.0 range with increasing x. This difference may be attributed to the structural differences in the storage phase. The pressure− composition−temperature (PCT) analysis by Sieberts' method was applied to the OSM. Although PCT curves exhibited a remarkable decrease in hysteresis in the PSA process as x increased, the difference between onset and offset temperatures for each oxygen storage/release reaction broadened. A new evaluation method to optimize x of Ca 2−x Sr x AlMnO 5 and operating condition in the PSA process using the OSM was also examined. Plots of the pressure change required to release oxygen versus the amount of oxygen extracted allow for the efficient determination of optimal composition and working temperature. Ca 1.2 Sr 0.8 AlMnO 5 (x = 0.80), which exhibited excellent repetition durability, was found to be optimal in this evaluation. The ideal PSA oxygen separation process using Ca 1.2 Sr 0.8 AlMnO 5 has the potential for producing pure oxygen with an energy input of 109.6 kWh/kNm 3 -O 2 , which is a significant energy saving compared to conventional processes.

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Section: Introductionmentioning

confidence: 99%

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Tanahashi

Omura

Naya

et al. 2021

ACS Sustainable Chem. Eng.

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“…There are examples in the literature in which the substitution by Ti in the Bs ublattice was used to improvet he redox and structural stabilityo fp erovskite materials under reducing conditions (e.g.,R efs. [46][47][48]). The approache mployed in this work is to introduce Ti into the Vs ublattice of SrVO 3 to enhanceits stability under more oxidizing conditions.…”

Section: Introductionmentioning

confidence: 99%

Compromising Between Phase Stability and Electrical Performance: SrVO₃–SrTiO₃ Solid Solutions as Solid Oxide Fuel Cell Anode Components

et al. 2018

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The applicability of perovskite‐type SrVO3−δ in high‐temperature electrochemical energy conversion technology is hampered by the limited stability domain of the perovskite phase. The aim of the present work was to find a compromise between the phase stability and electrical performance by designing solid solutions in the SrVO3–SrTiO3 system. Increasing titanium content in SrV1−yTiyO3−δ (y=0–0.9) perovskites is demonstrated to result in a gradual shift of the upper‐p(O2) phase stability boundary toward oxidizing conditions: from ≈10−15 bar at 900 °C for undoped SrVO3−δ to ≈10−11–10−5 bar for y=0.3–0.5. Although the improvement in the phase stability is accompanied by a decrease in electrical conductivity, the conductivities of SrV0.7Ti0.3O3−δ and SrV0.5Ti0.5O3−δ at 900 °C remain as high as 80 and 20 S cm−1, respectively, and is essentially independent of p(O2) within the phase‐stability domain. Combined XRD, thermogravimetric analysis, and electrical studies revealed very sluggish kinetics of oxidation of SrV0.5Ti0.5O3−δ ceramics under inert gas conditions and a nearly reversible behavior after exposure to an inert atmosphere at elevated temperatures. Substitution by titanium in the SrV1−yTiyO3−δ system results also in a decrease of oxygen deficiency in perovskite lattice and a favorable suppression of thermochemical expansion. Variations of oxygen nonstoichiometry and electrical properties in the SrV1−yTiyO3−δ series are discussed in combination with the simulated defect chemistry of solid solutions.

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“…Perovskite oxides, which have the formula ABO 3 , are functional ceramics used as cathodes in solid oxide fuel cells, , phosphors, , catalysts, oxygen permeable membranes, , and oxygen storage materials (OSMs). , In general, 3d transition metals are often substituted into the B-sites of these materials to tune their properties and make them useful for different applications as transition metals have different oxidation states and an aliovalent substitution can lead to oxygen nonstoichiometry. In addition, due to the wide variety of elements that can be substituted into the B-sites of perovskite oxides, such as the 3d and 4d transition metals and lanthanides (except for lanthanum), materials with different properties can be produced.…”

Section: Introductionmentioning

confidence: 99%

Effects of the Crystal Host Structure on the Oxygen Desorption Behavior in Perovskite-Type AeFe_0.9In_0.1O_3−δ (Ae = Sr and Ba)

et al. 2021

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The relationship between the oxygen desorption properties and changes in the electronic state of Fe ions and the local atomic structures of the Fe–O polyhedra in perovskite-type AeFe0.9In0.1O3−δ (Ae = Sr (SFI010) and Ba (BFI010)) upon varying the A-site ions was investigated. Thermogravimetry showed that oxygen was released from both materials above 440 °C in air, suggesting charge compensation via the reduction of Fe ions. Changes in the Fe valences were greater for SFI010 than BFI010. On heating both samples in air, Fe K-edge X-ray absorption spectroscopy (XAS) spectra continuously changed, arising from the change in the symmetry of the local atomic structures of the Fe–O polyhedra. The influence of the reduction of the Fe ions on the XAS spectra was considered to be a charge compensation for oxygen desorption above 440 °C. With increasing temperature, the local atomic structure of the Fe ions in SFI010 changed whereas that of BFI010 barely changed, although the crystal structures of both were retained during oxygen desorption. High structural tolerance for large changes in the local structure and lower Fe valence at high temperatures were observed in SFI010 and allowed for high oxygen desorption. Therefore, the electronic state at high temperatures and the retention of the crystal structure are important factors for preparing superior oxygen storage materials.

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Oxygen Storage Property and Chemical Stability of SrFe_1–xTi_xO_3−δ with Robust Perovskite Structure

Cited by 29 publications

References 38 publications

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Compromising Between Phase Stability and Electrical Performance: SrVO₃–SrTiO₃ Solid Solutions as Solid Oxide Fuel Cell Anode Components

Effects of the Crystal Host Structure on the Oxygen Desorption Behavior in Perovskite-Type AeFe_0.9In_0.1O_3−δ (Ae = Sr and Ba)

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Oxygen Storage Property and Chemical Stability of SrFe1–xTixO3−δ with Robust Perovskite Structure

Cited by 29 publications

References 38 publications

Sr-Doped Ca2AlMnO5 + δ for Energy-Saving Oxygen Separation Process

Sr-Doped Ca2AlMnO5 + δ for Energy-Saving Oxygen Separation Process

Compromising Between Phase Stability and Electrical Performance: SrVO3–SrTiO3 Solid Solutions as Solid Oxide Fuel Cell Anode Components

Effects of the Crystal Host Structure on the Oxygen Desorption Behavior in Perovskite-Type AeFe0.9In0.1O3−δ (Ae = Sr and Ba)

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Oxygen Storage Property and Chemical Stability of SrFe_1–xTi_xO_3−δ with Robust Perovskite Structure

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Sr-Doped Ca₂AlMnO_5 + δ for Energy-Saving Oxygen Separation Process

Compromising Between Phase Stability and Electrical Performance: SrVO₃–SrTiO₃ Solid Solutions as Solid Oxide Fuel Cell Anode Components

Effects of the Crystal Host Structure on the Oxygen Desorption Behavior in Perovskite-Type AeFe_0.9In_0.1O_3−δ (Ae = Sr and Ba)