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Title: Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (δ = 0.0905)

Abstract

The results of the synthesis and characterization of the optimally doped La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4-δ} solid solution with x = 0, 0.1, 0.2 and 0.3 are reported. The versatility of these La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} materials is explained on the basis of structural features and the ability to accommodate oxygen nonstoichiometry. According to powder X-ray and neutron diffraction data, La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} adopts the tetragonal structure with oxygen vacancies occurring preferentially at the O{sub ap} sites within the {(La/Ca)O} layers of the perovskite blocks and the oxygen deviation from stoichiometry δ was found to be δ=0.0905(6). The bulk conductivity indicated an Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at T=270 °C. An increase of the conductivity was detected when Ni was introduced. With nickel ratio variation, a strong correlation was observed between the Cu(Ni)-O{sub ap} apical bond length variation and the conductivity variation through controlling the O{sup 2−} ion migration. - Highlights: • We report the synthesis and structure of the La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (0≤x≤0.3; δ=0.0905) compounds. • La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (x=0.0, 0.2, 0.3) doped with Ni{sup 2+} have a highermore » conductivity than undoped La{sub 1.85}Ca{sub 0.15}CuO{sub 4−δ}. • At T=270 °C, sample x=0.3 has the highest conductivity (0.2915 sm{sup −1}).« less

Authors:
 [1];  [2];  [1];  [3];  [4];  [5]; ;  [6];
  1. Useful Materials Valorization Laboratory, National Centre of Research in Materials Science, Technologic Park of Borj Cedria, B.P. 73, 8027 Soliman (Tunisia)
  2. (Tunisia)
  3. (UR11ES85), Faculté des Sciences de Gabès/Université de Gabès, Campus Universitaire Cité Erriadh, Gabès 6072 (Tunisia)
  4. Laboratoire de Physico-Chimie des Matériaux Minéraux et leurs Applications, CNRSM, Technopole de Borj Cedria, B.P. 95, Hammam-Lif 2050 (Tunisia)
  5. Laboratoire de Cristallographie, CNRS, 25 Avenue des Martyrs, BP 166, 3804 Grenoble Cedex 9 (France)
  6. Institut de Chimie Moléculaire et des Matériaux – UMR 5253 – ICG C2M: Chimie et Cristallochimie des Matériaux, Université de Montpellier 2, Case courrier 01504 Place Eugène Bataillon, Bat 15, F-34095 Montpellier cedex 5 (France)
Publication Date:
OSTI Identifier:
22584184
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 240; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOND LENGTHS; CHARGE CARRIERS; DOPED MATERIALS; IONIC CONDUCTIVITY; LAYERS; MIGRATION; NEUTRON DIFFRACTION; NICKEL IONS; OXIDES; OXYGEN; PEROVSKITE; POWDERS; SOLID OXIDE FUEL CELLS; SOLID SOLUTIONS; SOLIDS; SYNTHESIS; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Midouni, Adnene, Université de Tunis El Manar, Campus Universitaire Farhat Hached, B.P. No 94- Rommana, 1068 Tunis, Houchati, Mohamed Ikbal, E-mail: ikb_med@yahoo.fr, Unité de Recherche Catalyse et Matériaux pour l’Environnement et les Procédés URCMEP, Othman, Walid Belhaj, Chniba-Boudjada, Nassira, Ceretti, Monica, Paulus, Werner, and and others. Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (δ = 0.0905). United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.05.017.
Midouni, Adnene, Université de Tunis El Manar, Campus Universitaire Farhat Hached, B.P. No 94- Rommana, 1068 Tunis, Houchati, Mohamed Ikbal, E-mail: ikb_med@yahoo.fr, Unité de Recherche Catalyse et Matériaux pour l’Environnement et les Procédés URCMEP, Othman, Walid Belhaj, Chniba-Boudjada, Nassira, Ceretti, Monica, Paulus, Werner, & and others. Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (δ = 0.0905). United States. doi:10.1016/J.JSSC.2016.05.017.
Midouni, Adnene, Université de Tunis El Manar, Campus Universitaire Farhat Hached, B.P. No 94- Rommana, 1068 Tunis, Houchati, Mohamed Ikbal, E-mail: ikb_med@yahoo.fr, Unité de Recherche Catalyse et Matériaux pour l’Environnement et les Procédés URCMEP, Othman, Walid Belhaj, Chniba-Boudjada, Nassira, Ceretti, Monica, Paulus, Werner, and and others. 2016. "Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (δ = 0.0905)". United States. doi:10.1016/J.JSSC.2016.05.017.
@article{osti_22584184,
title = {Influence of nickel doping on oxygen-ionic conductivity of the n = 1 Ruddlesden-Popper Phases La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (δ = 0.0905)},
author = {Midouni, Adnene and Université de Tunis El Manar, Campus Universitaire Farhat Hached, B.P. No 94- Rommana, 1068 Tunis and Houchati, Mohamed Ikbal, E-mail: ikb_med@yahoo.fr and Unité de Recherche Catalyse et Matériaux pour l’Environnement et les Procédés URCMEP and Othman, Walid Belhaj and Chniba-Boudjada, Nassira and Ceretti, Monica and Paulus, Werner and and others},
abstractNote = {The results of the synthesis and characterization of the optimally doped La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4-δ} solid solution with x = 0, 0.1, 0.2 and 0.3 are reported. The versatility of these La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} materials is explained on the basis of structural features and the ability to accommodate oxygen nonstoichiometry. According to powder X-ray and neutron diffraction data, La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} adopts the tetragonal structure with oxygen vacancies occurring preferentially at the O{sub ap} sites within the {(La/Ca)O} layers of the perovskite blocks and the oxygen deviation from stoichiometry δ was found to be δ=0.0905(6). The bulk conductivity indicated an Arrhenius-type thermally activated process and oxygen vacancies are the possible ionic charge carriers at T=270 °C. An increase of the conductivity was detected when Ni was introduced. With nickel ratio variation, a strong correlation was observed between the Cu(Ni)-O{sub ap} apical bond length variation and the conductivity variation through controlling the O{sup 2−} ion migration. - Highlights: • We report the synthesis and structure of the La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (0≤x≤0.3; δ=0.0905) compounds. • La{sub 1.85}Ca{sub 0.15}(Cu{sub 1−x}Ni{sub x})O{sub 4−δ} (x=0.0, 0.2, 0.3) doped with Ni{sup 2+} have a higher conductivity than undoped La{sub 1.85}Ca{sub 0.15}CuO{sub 4−δ}. • At T=270 °C, sample x=0.3 has the highest conductivity (0.2915 sm{sup −1}).},
doi = {10.1016/J.JSSC.2016.05.017},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 240,
place = {United States},
year = 2016,
month = 8
}
  • The authors have synthesized two new lithium-containing oxides which are related to Ruddlesden-Popper phases, Li{sub 4}Sr{sub 3}Nb{sub 5.77}Fe{sub 0.23}O{sub 19.77} and Li{sub 4}Sr{sub 3}Nb{sub 6}O{sub 20}, with partial occupancy of the 12-coordinated sites by Sr, for the first time by direct solid-state reaction. While the single crystal and powder X-ray diffraction data indicate that these oxides crystallize in tetragonal cells (space group I4/mmm; a = 3.9585(2) {angstrom}, c = 25.915(3) {angstrom} and a = 3.953(2) {angstrom}, c = 26.041(5) {angstrom} for the respective oxides), the electron diffraction of some of the crystallites shows supercell reflections with a {approx} {radical}2a{sub p},more » c {approx} 25.9 {angstrom}, probably indicating a twisting of the NbO{sub 6} octahedra in the ab-plane. Although, these oxides show no significant lithium ionic conduction at room temperature, they show distinct conductivity values at elevated temperatures.« less
  • Through alignment of theoretical modeling with experimental measurements of oxygen surface-exchange kinetics on (001)-oriented La 2–xSr xMO 4+δ (M = Co, Ni, Cu) thin films, we demonstrate here the capability of the theoretical bulk O 2p-band centers to correlate with oxygen surface-exchange kinetics of the Ruddlesden–Popper oxide (RP 214) (001)-oriented thin films. In addition, we demonstrate that the bulk O 2p-band centers can also correlate with the experimental activation energies for bulk oxygen transport and oxygen surface exchange of both the RP 214 and the perovskite polycrystalline materials reported in the literature, indicating the effectiveness of the bulk O 2p-bandmore » centers in describing the associated energetics and kinetics. Here, we propose that the opposite slopes of the bulk O 2p-band center correlations between the RP 214 and the perovskite materials are due to the intrinsic mechanistic differences of their oxygen surface-exchange kinetics bulk anionic transport.« less
  • There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of threemore » Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less
  • The room-temperature crystal structures of the n = 3 Ruddlesden-Popper phases Ca/{sub 4}-Mn{sub 2}FeO{sub 9.75} and Sr{sub 4}Mn{sub 2}FeO{sub 9.80} have been refined from neutron and X-ray powder diffraction data. Both adopt space group I4/mmm with (a,c) = (Ca, 3.73683(1), 27.0860(1) {angstrom}), (Sr, 3.83393(1), 27.8148(1) {angstrom}). In both compounds the cation site at the center of the perovskite blocks is preferentially occupied by Fe (Ca, Mn:Fe = 0.424:0.576(4)), and the anion vacancies are found around this site. The occupied anion sites show static disorder in Ca{sub 4}Mn{sub 2}FeO{sub 9.75} but not in Sr{sub 4}Mn{sub 2}FeO{sub 9.80}. Both compounds are electricalmore » insulators which order antiferromagnetically at T{sub N} = 75 K (Ca) or 90 K (Sr). Susceptibility and M(H) data suggest that not all the Mn and Fe cations take part in the long-range magnetic ordering, and there is evidence of a spin glass transition in both compounds at {approximately}11 K. The magnetic structure of Ca{sub 4}Mn{sub 2}FeO{sub 9.75} at 5 K has been determined by neutron diffraction. No ordered moment was detected on the Mn/Fe site at the center of the perovskite blocks; 0.74(1) {micro}{sub B} per transition metal cation was measured at the sites on the block edges. Possible causes of magnetic frustration in this crystal structure are considered. Ca{sub 4}Mn{sub 2}FeO{sub 9.75} has a magnetoresistance of {minus}4% at 137 K in a 14 T field.« less
  • The crystal chemistry of the system LaO{sub 1.5}-CaO-CuO at the 1:1:2 composition was studied at high pressures with the goal of stabilizing new perovskite cuprates with two-dimensional ordering of La, Ca cations and oxygen vacancies. Several phases, including the perovskites La{sub 4}Ca{sub 4}Cu{sub 8}O{sub 20}, La{sub 4}Ca{sub 4}Cu{sub 88}O{sub 18} and the Ruddlesden-Popper (RP) phase La{sub 2}Ca{sub 2}Cu{sub 3}O{sub 8}, containing three copper oxide layers (n = 3), were revealed for the first time. The results are very sensitive to experimental conditions, and a variety of reaction channels are observed at the 1:1:2 composition depending on the choice of totalmore » pressure, p{sub O}{sub 2}, temperature, and annealing conditions. The perovskite-related phases at this composition exhibited A-site cation disorder and three-dimensional ordering of oxygen vacancies. The Ruddlesden-Popper phase required the substitution of Sr on the A-sites to be metastably retained at room temperature. Due to its thermal instability, the RP phase could not be doped to a carrier concentration at which superconductivity might be observed.« less