Browsing by Author "Frade, JR"

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    Behavior of (La,Sr)CoO3- and La2NiO4-based ceramic anodes in alkaline media: compositional and microstructural factors
    (Springer, 2008-01) Poznyak, SK; Kharton, VV; Frade, JR; Yaremchenko, AA; Tsipis, EV; Yakovlev, SO; Marozau, IP
    The behavior of dense ceramic anodes made of perovskite-type La1-x-ySrxCo1-zAlzO3-δ (x=0.30-0.70; y=0-0.05; z=0-0.20) and K2NiF4- type La2Ni1-xMexO4+δ (Me=Co, Cu; x=0-0.20) indicates significant influence of metal hydroxide formation at the electrode surface on the oxygen evolution reaction (OER) kinetics in alkaline solutions. The overpotential of cobaltite electrodes was found to decrease with time, while cyclic voltammetry shows the appearance of redox peaks characteristic of Co(OH)(2)/CoOOH. This is accompanied with increasing effective capacitance estimated from the impedance spectroscopy data, because of roughening of the ceramic surface. The steady-state polarization curves of (La,Sr)CoO3-δ in the OER range, including the Tafel slope, are very similar to those of model Co(OH)(2)-La(OH)(3) composite films where the introduction of lanthanum hydroxide leads to decreasing electrochemical activity. La2NiO4-based anodes exhibit a low electrochemical performance and poor stability. The effects of oxygen nonstoichiometry of the perovskite-related phases are rather negligible at high overpotentials but become significant when the polarization decreases, a result of increasing role of oxygen intercalation processes. The maximum electrocatalytic activity to OER was observed for A-site-deficient (La0.3Sr0.7)(0.97)CoO3-δ, where the lanthanum content is relatively low and the Co4+ concentration determined by thermogravimetric analysis is highest compared to other cobaltites. Applying microporous layers made of template-synthesized nanocrystalline (La0.3Sr0.7)(0.97)CoO3-δ leads to an improved anode performance, although the effects of microstructure and thickness are modest, suggesting a narrow electrochemical reaction zone. Further enhancement of the OER kinetics can be achieved by electrodeposition of cobalt hydroxide- and nickel hydroxide- based films. © 2008, Springer.
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    Chemically induced expansion of La2NiO4+ δ-based materials
    (American Chemical Society, 2007-03-21) Kharton, VV; Kovalevsky, AV; Avdeev, M; Tsipis, EV; Patrakeev, MV; Yaremchenko, AA; Naumovich, EN; Frade, JR
    The equilibrium chemical strains induced by the oxygen hyperstoichiometry variations in mixed-conducting La2Ni1-xMxO4+δ (M = Fe, Co, Cu; x = 0−0.2) with K2NiF4-type structure, were studied by controlled-atmosphere dilatometry at 923−1223 K in the oxygen partial pressure range 5 × 10-4 to 0.7 atm. In combination with the oxygen content measured by coulometric titration and thermogravimetry, the results reveal a very low chemical expansivity, favorable for high-temperature electrochemical applications. Under oxidizing conditions, the isothermal expansion relative to atmospheric oxygen pressure (εC) is less than 0.02%. The ratio between these values and the corresponding nonstoichiometry increment varies from −3 × 10-3 to 6 × 10-3, which is much lower compared to most permeable mixed conductors derived from perovskite-like cobaltites and ferrites. Consequently, the chemical contribution to apparent thermal expansion coefficients at a fixed oxygen pressure, (13.7−15.1) × 10-6 K-1, does not exceed 5%. The high-temperature X-ray diffraction studies showed that this behavior results from strongly anisotropic expansion of the K2NiF4-type lattice, namely the opposing variations of the unit-cell parameters on changing oxygen stoichiometry. © 2007, American Chemical Society
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    Mixed conductivity and stability of CaFe2O4−δ
    (Electrochemical Society, 2008-03) Kharton, VV; Tsipis, EV; Kolotygin, VA; Avdeev, M; Viskup, AP; Waerenborgh, JC; Frade, JR
    The total conductivity of CaFe2O4-delta, studied in the oxygen partial pressure range from 10(-17) to 0.5 atm at 1023-1223 K, is predominantly p-type electronic under oxidizing conditions. The oxygen ion transference numbers determined by the steady-state oxygen permeation and faradaic efficiency measurements vary in the range of 0.2 to 7.2 x 10(-4) at 1123-1273 K, increasing with temperature. No evidence of any significant cationic contribution to the conductivity was found. The Mossbauer spectroscopy, thermogravimetry, and X-ray diffraction (XRD) showed that the orthorhombic lattice of calcium ferrite is essentially intolerant to the oxygen vacancy formation and to doping with lower-valence cations, such as Co and Ni. The oxygen nonstoichiometry (delta) is almost negligible, 0.0046-0.0059 at 973-1223 K and p(O-2) = 10(-5)-0.21 atm, providing a substantial dimensional stability of CaFe2O4-delta ceramics. The average linear thermal expansion coefficients, calculated from the controlled-atmosphere dilatometry and high-temperature XRD data, are (9.6-13.9) x 10(-6) K-1 in the oxygen pressure range from 10(-8) to 0.21 atm at 873-1373 K. Decreasing P(02) results in a modest lattice contraction and in the p-n transition indicated by the conductivity and Seebeck coefficient variations. The phase decomposition of CaFe2O4-delta occurs at oxygen chemical potentials between the low-p(O-2) stability limit of Ca2Fe2O5-delta brownmillerite and the hematite/magnetite boundary in binary Fe-O system. © 2008, Electrochemical Society Inc.
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    Mixed conductivity, thermal expansion and defect chemistry of a-site deficient LaNi(0.5)Ji(0.5)O(3-delta)
    (Elsevier, 2007-03-19) Yakovlev, SO; Kharton, VV; Yaremchenko, AA; Kovalevsky, AV; Naumovich, EN; Frade, JR
    This work is focused on the analysis of defect chemistry and partial electronic and oxygen ionic conductivities of A-site deficient La1-xNi0.5Ti0.5O3-delta (x = 0.05 and 0.10). The orthorhombic-to-rhombohedral phase transition was monitored by means of dilatometry and high-temperature X-ray diffractometry. The average thermal expansion coefficients vary in the range (8.5-13.0) x 10(-6) K-1, increasing with temperature and A-site deficiency. The ion transference numbers determined by the Faradaic efficiency measurements are lower than 0.1% at 900-975 degrees C in air. Activation energies of the oxygen ionic conductivity at 897-977 degrees C are 430 and 220 kJ/mol for x = 0.05 and 0.10, respectively. Atomistic simulation demonstrated high stability of ternary defect clusters formed by the vacant sites in the A-sublattice, oxygen vacancies and W, cations, which leads to a very low level of mixed conductivity. © 2007, Elsevier Ltd.
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    Oxygen permeability, stability and electrochemical behavior of Pr2NiO4+δ-based materials
    (Springer, 2007-08) Kovalevsky, AV; Kharton, VV; Yaremchenko, AA; Pivak, YV; Tsipis, EV; Yakovlev, SO; Markov, AA; Naumovich, EN; Frade, JR
    The high-temperature electronic and ionic transport properties, thermal expansion and stability of dense Pr2NiO4+δ Pr2Ni0.9Fe0.1O4+δ ceramics have been appraised in comparison with K2NiF4-type lanthanum nickelate. Under oxidizing conditions, the extensive oxygen uptake at temperatures below 1073-1223 K leads to reversible decomposition of Pr2NiO4-based solid solutions into Ruddlesden-Popper type Pr4Ni3O10 and praseodymium oxide phases. The substitution of nickel with copper decreases the oxygen content and phase transition temperature, whilst the incorporation of iron cations has opposite effects. Both types of doping tend to decrease stability in reducing atmospheres as estimated from the oxygen partial pressure dependencies of total conductivity and Seebeck coefficient. The steady-state oxygen permeability of Pr2NiO4+δ ceramics at 1173-1223 K, limited by both surface-exchange kinetics and bulk ionic conduction, is similar to that of La2NiO4+δ. The phase transformation on cooling results in considerably higher electronic conductivity and oxygen permeation, but is associated also with significant volume changes revealed by dilatometry. At 973-1073 K, porous Pr2Ni0.8Cu0.2O4+δ electrodes deposited onto lanthanum gallate-based solid electrolyte exhibit lower anodic overpotentials compared to Pr2Ni0.8Cu0.2O4+δ, whilst cathodic reduction decreases their performance. © 2007, Springer.