Evaluating oxygen diffusion, surface exchange and oxygen semi-permeation in Ln2NiO4+δ membranes (Ln=La, Pr and Nd)

Geffroy, Pierre-Marie; Reichmann, Mickaël; Chartier, Thierry; Bassat, Jean‐Marc; Grenier, Jean‐Claude

doi:10.1016/j.memsci.2013.08.035

Cited by 30 publications

(13 citation statements)

References 29 publications

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“…For LnCNO materials a high oxygen mobility (D * ~10 -7 cm 2 /s at 700°C) was demonstrated. This is provided by the cooperative mechanism of its migration involving both interstitial and regular oxygen [12,13]. Doping with Ca decreases oxygen mobility due to decreasing the interstitial oxygen content as charge compensation and increasing the energy barrier for oxygen jumps between the interstitial and apical positions in octahedral layers due to cationic size effect.…”

Section: Oxygen Mobility and Surface Reactivitymentioning

confidence: 99%

“…Ruddlesden -Popper phases (RP) are promising due to their moderate thermal expansion coefficients and a high mixed ionic-electronic conductivity. A high oxygen mobility of these materials (oxygen tracer diffusion coefficient ~10 -7 cm 2 /s at 700°C) is provided by the cooperative mechanism of its migration involving both regular and highly mobile interstitial oxygen of perovskite and rock salt layers, respectively [5,[11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

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Design of materials for solid oxide fuel cells cathodes and oxygen separation membranes based on fundamental studies of their oxygen mobility and surface reactivity

et al. 2019

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Design of materials for solid oxide fuel cells cathodes and oxygen separation membranes and studying their oxygen transport characteristics are important problems of modern hydrogen energy. In the current work, fundamentals of such materials design based on characterization of their oxygen mobility by oxygen isotope exchange with C18O2 and 18O2 in flow and closed reactors for samples of Ruddlesden – Popper-type oxides Ln2-xCaxNiO4+δ, perovskite-fluorite nanocomposites PrNi0.5Co0.5O3-δ – Ce0.9Y0.1O2-δ, etc. are presented. Fast oxygen transport was demonstrated for PNC – YDC (DO ~10-8 cm2/s at 700°C) nanocomposites due to domination of the fast diffusion channel involving oxygen of the fluorite phase with incorporated Pr cations and developed perovskite-fluorite interfaces. For LnCNO materials a high oxygen mobility (DO ~10-7 cm2/s at 700°C) provided by the cooperative mechanism of its migration was demonstrated. Depending on Ca dopant content and Ln cation nature, in some cases 1–2 additional channels of the slow diffusion appear due to decreasing the interstitial oxygen content and increasing the energy barrier for oxygen jumps due to cationic size effect. Optimized by the chemical composition and nanodomain structure materials of these types demonstrated a high performance as SOFC cathodes and functional layers in asymmetric supported oxygen separation membranes.

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Section: Oxygen Mobility and Surface Reactivitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Design of materials for solid oxide fuel cells cathodes and oxygen separation membranes based on fundamental studies of their oxygen mobility and surface reactivity

et al. 2019

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“…Additionally, the map is modified in relation to other parameters, such as the microstructure, thickness of the membrane, and temperature. The oxygen transport is predominately governed by oxygen diffusion at high temperatures and by oxygen surface exchange at low temperatures [13,20]. The microstructure can strongly affect the mechanism of oxygen transport, as suggested in our recent work [21].…”

Section: Electrical Conductivity Of Lamentioning

confidence: 99%

Identification of the rate-determining step in oxygen transport through La(1−x)SrxFe(1−y)GayO3−δ perovskite membranes

Geffroy

Reichmann

Kilmann

et al. 2015

Journal of Membrane Science

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“…Pr 2 NiO 4+δ oxide with a layered Ruddlesden-Popper (R-P) structure is a promising material for SOFC cathodes [1][2][3][4][5][6][7][8], electrodes for electrolysers and reversible cells [9,10] and oxygen separation membranes [11][12][13][14] due to a high oxygen mobility provided by the cooperative mechanism of oxygen migration involving both interstitial oxygen species and apical oxygen of the NiO 6 octahedra, as well as intermediate values of thermal expansion coefficients (TECs) and stability to carbonization [3,5,11,[15][16][17][18][19][20]. Doping is usually applied to diminish Pr 2 NiO 4+δ phase instability in the temperature range of 850-1000°C [21].…”

Section: Introductionmentioning

confidence: 99%

Oxygen transport in Pr nickelates: Elucidation of atomic-scale features

et al. 2020

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Pr 2 NiO 4+δ oxide with a layered Ruddlesden-Popper structure is a promising material for SOFC cathodes and oxygen separation membranes due to a high oxygen mobility provided by the cooperative mechanism of oxygen migration involving both interstitial oxygen species and apical oxygen of the NiO 6 octahedra. Doping by Ca improves thermodynamic stability and increases electronic conductivity of Pr 2−x Ca x NiO 4+δ , but decreases oxygen mobility due to decreasing the oxygen excess and appearing of 1-2 additional slow diffusion channels at x ≥ 0.4, probably, due to hampering of cooperative mechanism of migration. However, atomic-scale features of these materials determining oxygen migration require further studies. In this work characteristics of oxygen diffusion in Pr 2−x Ca x NiO 4+δ (x = 0-0.6) are compared with results of the surface analysis by X-ray photoelectron spectroscopy and modeling of the interstitial oxygen migration by the plane-wave density functional theory calculations. According to the X-ray photoelectron spectroscopy data, the surface is enriched by Pr for undoped sample and by Ca for doped ones. The O1s peak at~531 eV corresponding to a weakly bound form of surface oxygen located at Pr cations disappears at~500°C. Migration of interstitial oxygen was modeled for a I4/mmm phase of Pr 2 NiO 4+δ . The interstitial oxygen anion repulses the apical one in the NiO 6 octahedra pushing it into the tetrahedral site between Pr cations. The calculated activation barrier of this migration is equal to 0.585 eV, which reasonably agrees with the experimental value of 0.83 eV obtained by the oxygen isotope exchange method. At the same time, for the model compound Ca 2 NiO 4+δ , obtained by isomorphic substitution of Pr by Ca in Pr 2 NiO 4+δ , calculations implied formation of the peroxide ion comprised of interstitial and lattice oxygen species not revealed in the case of incomplete substitution (up to PrCaNiO 4+δ composition).Hence, calculations in the framework of the plane-wave density functional theory provide a realistic estimation of specificity of oxygen migration features in Pr 2 NiO 4+δ doped by alkaline-earth metals.

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Evaluating oxygen diffusion, surface exchange and oxygen semi-permeation in Ln2NiO4+δ membranes (Ln=La, Pr and Nd)

Cited by 30 publications

References 29 publications

Design of materials for solid oxide fuel cells cathodes and oxygen separation membranes based on fundamental studies of their oxygen mobility and surface reactivity

Design of materials for solid oxide fuel cells cathodes and oxygen separation membranes based on fundamental studies of their oxygen mobility and surface reactivity

Identification of the rate-determining step in oxygen transport through La(1−x)SrxFe(1−y)GayO3−δ perovskite membranes

Oxygen transport in Pr nickelates: Elucidation of atomic-scale features

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