Zirconia stabilized by Y and Mn: A microstructural characterization

Cubic stabilized ZrO₂ with 8 mol% Y₂O₃ (YSZ) is commonly used as an electrolyte in solid oxide fuel cells (SOFC). One of the most promising cathode materials is La,Sr-manganite (LSM). During manufacture and operation of the SOFC, Mn diffuses from the LSM into YSZ. The structural changes caused by the presence of Mn in the electrolyte under various oxygen partial pressures have been examined by X-ray diffraction. Microstructures of YSZ containing Mn have been examined by transmission electron microscopy and surface changes of the electrolyte due to Mn diffusion were studied by scanning electron microscopy. The results are discussed with respect to properties and stability of the electrolyte and the SOFC. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

8YSZ/(La0.8Sr0.2)0.95MnO3-δ cathode performance at 1-3 bar oxygen pressures

Pressurised operation of solid oxide fuel cells (SOFC) has been shown to significantly improve their performance (Singhal, 2000) [1], however little work has been done on the effects of pressure on SOFC cathodes. The effect of pressurised oxygen on the area specific polarisation resistance (ASRp) of (La_0.8Sr_0.2)_0.95MnO_3-δ/8YSZ SOFC cathodes was determined by electrochemical impedance spectroscopy (EIS). Pellets of 8YSZ were pressed and sintered at 1350 °C, and screen printed layers of LSM/8YSZ cathode and LSM current collector were applied and sintered at 1300 °C and 1200 °C respectively. EIS was carried out between 1 and 3 bar oxygen at 800-1000 °C. One process dominated the spectra, and was identified as process C, (Jorgensen and Morgensen, 2001) [2] by comparison of measured and reference frequency maxima, the dependence of polarisation resistance on P_O2, the capacitance, and the activation energy. It is suggested that this represents the physical process of dissociative adsorption of oxygen at the triple phase boundaries of the electrode. A second process, with a magnitude almost independent of P_O2, is observed, which may be process B [2], related to transport of oxygen ions in the YSZ.     

Electrochemical characterization of mixed conducting and composite SOFC cathodes

The electrochemical performance of La_0.58Sr_0.4Co_0.2Fe_0.8O_3−δ (L58SCF), La_0.9Sr_1.1FeO_4−δ (LS2F) and LSM (La_0.65Sr_0.3MnO_3−δ)/LSM–YSZ (50 wt.% LSM–50 wt.% ZrO₂ (8 mol% Y₂O₃)) cathode electrodes interfaced to a double layer Ce_0.8Gd_0.2O_2−δ (CGO)/YSZ electrolyte was studied in the temperature range of 600 to 850 °C and under flow of 21% O₂/He mixture, using impedance spectroscopy and current density–overpotential measurements. The L58SCF cathode exhibited the highest electrocatalytic activity for oxygen reduction, according to the order: LS2F/CGO/YSZ ≤ LSM/LSM–YSZ/CGO/YSZ < L58SCF/CGO/YSZ.     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Composite (La,Sr)MnO3–YSZ cathode for SOFC

(La, Sr)MnO₃ (LSM)–Y doped ZrO₂ (YSZ) composite was prepared using YSZ colloidal suspension (initial YSZ particle size ∼100 nm), YSZ and LSM polymer precursors on dense substrates at 800 °C annealing temperature. The results of a symmetrical LSM–YSZ composite cell test showed the area specific resistance for overpotential of 0.14 Ω cm² at 800 °C, which indicated that the LSM–YSZ composite could be a potential candidate for cathode in SOFCs. The performance of the cell with the LSM–YSZ composite cathode and Ni-YSZ anode was investigated and the power density of about 0.26 W cm^− 2 was obtained at 850 °C using hydrogen fuel.     

Morphology Control of the Electrode for Solid Oxide Fuel Cells by Using Nanoparticles

LSM(La(Sr)MnO₃)/YSZ(Y₂O₃ stabilized ZrO₂) composite cathode for Solid Oxide Fuel Cells (SOFCs) was fabricated by using the composite particle consisting of well-dispersed nano-size grains of LSM and YSZ. The composite cathode had a porous structure as well as uniformly dispersed fine LSM and YSZ grains. Such unique morphology of the composite cathode led high electrochemical activity at 800°C. It suggests that the intermediate temperature (less than 800°C) operation of SOFCs will be achieved by using composite particles.     

Impedance investigation on porous Sr-doped LaMnO<Subscript>3</Subscript> films onto Sr-Mg-doped LaGaO<Subscript>3</Subscript> electrolyte

The use of Sr-Mg-doped LaGaO₃ (LSGM), a highly conducting oxygen ion electrolyte, in intermediate temperature solid oxide fuel cells (IT-SOFC) technology requires suitable electrode materials. Because the Sr-doped LaMnO₃ (LSM) cathode coupled with the YSZ electrolyte had shown relatively good performances, it has been also suggested for LSGM-based cells. As cathode overpotential is the main performance limitation, the optimization of the LSM/LSGM interface might be of fundamental relevance in the technology development of LSGM-based IT-SOFC. LSM films with different porosities were screen printed on both faces of the LSGM pellets; their morphology and electrical properties were investigated by scanning electron microscopy and impedance spectroscopy, respectively. Porosity was induced by the addition of icing sugar (3–5 wt%) to the LSM powder during ink preparation. Homogeneous electrode layers with a thickness of about 30 μm were obtained. The higher the sugar amount, the higher the film porosity and the lower the LSM grain size. The Nyquist plots show two low frequency arcs to which the charge transfer and mass transfer process or oxygen dissociation process were associated, respectively. One can expect that the best electrochemical performances are obtained using highly porous electrode. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Microstructural studies on degradation of interface between LSM–YSZ cathode and YSZ electrolyte in SOFCs

The changes in the cathode/electrolyte interface microstructure have been studied on anode-supported technological solid oxide fuel cells (SOFCs) that were subjected to long-term (1500 h) testing at 750 °C under high electrical loading (a current density of 0.75 A/cm²). These cells exhibit different cathode degradation rates depending on, among others, the composition of the cathode gas, being significantly smaller in oxygen than in air. FE-SEM and high resolution analytical TEM were applied for characterization of the interface on a submicron- and nano-scale. The interface degradation has been identified as the loss of LSM coverage and the loss of three-phase-boundary (TPB) length. Firstly, the degradation is caused by the size reduction of the individual LSM/YSZ electrolyte contact points (areas) that are initially of 100–200 nm in diameter. Quantitative microstructure evaluation shows that in the cell tested in air this mechanism contributes to an estimated overall reduction in the LSM coverage and the TPB length by 50 and 30%, respectively. For the cell tested in oxygen the corresponding values are 10 and 4%. Secondly, in the cell tested in air the LSM coverage and the TPB length appear to decrease further due to the more pronounced formation of insulating zirconate phases that are present locally and preferably in LSM/YSZ electrolyte contact areas. The effects of the cathode gas on the interface degradation are discussed considering the change of oxygen activity at the interface, possible changes in the Mn diffusion pattern as well as the LSM/YSZ reactivity. Finally, based on thermodynamic calculations a T–p(O₂) diagram predicting the safe and risky operation conditions in terms of the zirconate formation is presented and compared with the experimental observations.     

Effect of palladium oxidation state on the kinetics and mechanism of the charge transfer reaction taking place at the Pd/YSZ interface

Electrode polarization and conductivity measurements were carried out at the Pd/YSZ interface and at conditions close to the Pd–PdO thermodynamic equilibrium. The steady-state current–overpotential characteristics were analyzed with a Butler–Volmer type of equation. Both, apparent exchange current density, I_o, and anodic/cathodic charge transfer coefficients (α_a/α_c), were calculated. Based on the experimental results, it was concluded that the charge transfer at the electrode is rate-determining in the case of PdO during anodic operation and Pd during cathodic operation, while in the other case mass transport of adsorbed oxygen species along the electrode/solid electrolyte interface is in competition with the charge transfer process.     

Oxygen electrodes of zirconia electrolytes: fundamentals and application to analysis of oxygen containing gases

The kinetics of the oxygen exchange reaction and the reduction of NO at La_0.8Sr_0.2CoO₃−, La_0.8Sr_0.2MnO₃− and Ag-electrodes on stabilized zirconia (8mol% Y₂0₃=YSZ) has been studied by means of electrochemical methods (impedance, I-U characteristics). For La_0.8Sr_0.2CoO₃ electrodes the oxygen exchange was found to proceed via the bulk of the electrode with a rate limiting oxygen exchange at the electrode surface. Electrodes based on La_0.8Sr_0.2MnO₃ change their electrode characteristics with the applied potential. At low cathodic polarization the electrode reaction is limited to the three-phase boundary electrode/YSZ/gas. At high cathodic potentials oxygen vacancies are created and consequently additional oxygen is exchanged via the electrode bulk. Furthermore, a significant NO reduction was observed which indicate a reaction with the oxygen vacancies at the electrode surface. For Ag a rate limiting transport of oxygen atoms through the bulk of the electrode was found. As a consequence the oxygen concentration at the electrode surface remains nearly constant. In this context, the observed inactivity for the NO reduction of Ag-electrodes may be explained. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Different types of vortex pinning contribution to critical current density in YBa2Cu3O7−δ /YSZ quasi-multilayer

The quasi-multilayer films of YBa₂Cu₃O_7−δ /YSZ (YSZ denotes Yttria Stabilized Zirconia) are prepared by means of pulsed laser deposition (PLD), and a systematic study of the magnetic-field and temperature dependence of the critical current density J _c(H,T) for the YBCO/YSZ quasi-multilayer film is presented. Angular-dependent J _c(H,T) measurements have demonstrated that the growth control strategy is very effective in preventing the vortex motion at high fields and high temperatures. The temperature dependence of isotropic and anisotropic contribution to J _c is investigated in order to evaluate the strength of the defects. It is suggested that at high applied fields (such as 7 T), the pinning contribution of the YBCO/YSZ quasi-multilayer is dominated by the anisotropic disorders, while at intermediate-low fields (such as 1 and 3 T) the pinning contribution is determined by both isotropic and anisotropic disorders.     

Reaction mechanisms of the copper-manganese spinel cathode in a solid oxide fuel cell

Cu_1.25Mn_1.75O₄ spinel (CMO) was studied as a potential solid oxide fuel cell (SOFC) cathode material at intermediate temperatures. The reaction mechanism of a composite cathode consisting of Cu_1.25Mn_1.75O₄ and yttria-stabilized zirconia (YSZ) was investigated by impedance spectroscopy. The influence of the CMO/YSZ ratio, time exposed to current passage and temperature on the impedance spectra was examined. Activation energy of the corresponding processes was calculated to be near 1 eV and between 1.32 and 1.96 eV for the high and low frequency arcs in the impedance spectra. Comparison between CMO-YSZ and Sr-doped LaMnO₃ (LSM)-YSZ composite cathodes showed they had similar reaction mechanisms. The transport or transfer of oxygen intermediates or oxide ions between the catalyst and electrolyte was suggested to be the rate determining steps between 700 and 800 °C, whereas dissociative adsorption, mass transfer and surface diffusion were rate controlling between 600 and 700 °C.     

Josephson effect in superconducting constrictions with hybrid SF electrodes: Peculiar properties determined by the misorientation of magnetizations

Josephson current in SFcFS junctions with arbitrary transparency of the constriction (c) is investigated. The emphasis is on the analysis of the supercurrent dependencies on the misorientation angle θ between the in-plane magnetizations of diffusive ferromagnetic layers (F). It is found that the current-phase relation I(φ) may be radically modified with the θ variation: the harmonic I ₁ sin φ vanishes for a definite value of θ provided that, for an identical orientation of the magnetizations (θ = 0), the junction is in the “π” state. The Josephson current may exhibit a nonmonotonic dependence on the misorientation angle both for realization of the “0” and “π” state at θ = 0. We also analyze the effect of the exchange field induced enhancement of the critical current, which may occur in a definite range of θ. The text was submitted by the author in English.     

Spray pyrolysis of electrolyte interlayers for vacuum plasma-sprayed SOFC

The effects of gadolinia-doped ceria (CGO, Ce_0.8Gd_0.2O_1.9−x) and yttria-doped zirconia (8YSZ, Zr_0.92Y_0.08O_2−x) interlayers prepared by spray pyrolysis between vacuum plasma-sprayed 8YSZ electrolytes (8YSZ–VPS) and screen-printed (La_0.8Sr_0.2)_0.98MnO₃ cathodes (LSM) on the power output of solid oxide fuel cells (SOFC) are investigated. Amorphous thin films are deposited and then converted to nanocrystalline electrolyte–cathode interlayers during the first heat-up cycle of a SOFC to the operating temperature. CGO thin films between the YSZ plasma-sprayed electrolyte and the LSM cathode increased the power output by more than 20% compared to cells without interlayers, whereas YSZ films degraded the power output of cells. It is assumed that CGO improves the charge transfer at the electrolyte–cathode interface and that the CGO layer prevents the formation of undesirable insulation of La-zirconate at the interface 8YSZ/LSM.     

Josephson and single-particle currents between partially dielectricized superconductors with charge-density waves

The amplitudes of the nonstationary Josephson current I ¹, the interference current I ², and the quasiparticle current J through symmetric and asymmetric tunnel junctions, including superconductors with charge density waves, are calculated. In the symmetric (s) case the dependence of the Josephson current I _s ¹ on the voltage V on the junction has a logarithmic singularity at |eV|=2Δ, Δ+D, and 2D, where , Δ and Σ are the superconducting and dielectric order parameters, and e is the unit charge. At temperatures T≠0 jumps appear in the current-voltage characteristics I _s ¹ (V) at |eV|=D−Δ. Jumps and singularities are observed in the currents I _s ² and J _s at the same voltages at which singularities and jumps appear in I _s ¹ , respectively. In the nonsymmetric (ns) junctions which include an ordinary superconductor, singularities and jumps occur at |eV|=D+Δ_BCS, Δ+Δ_BCS, and (for T≠0) |D−Δ_BCS| and |Δ−Δ_BCS|, where Δ_BCS is the order parameter of an ordinary superconductor. The quasiparticle current J _ns is an asymmetric function of the voltage V and does not depend on the sign of Σ. The results are compared with experiment. Fiz. Tverd. Tela (St. Petersburg) 39, 991–999 (June 1997)     

Influence of electrical and optical losses on fundamental solar-cell parameters

Summary We present here an analysis of the dependence of the light-generated current on the current at maximum power in lossy solar cells. that is, cells with both series and shunt resistances present simultaneously — that is, a real cell. It is essentially seen that this dependence is highly sensitive to series resistance. However, for cells with series resistance of the order of 3 Ω, ϖI _g/ϖI _mp=1. We also look at the influence of TiO_x antireflection coatings on the open-circuit voltage and short-circuit current in silicon solar cells.

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Riassunto Si presenta un'analisi della dipendenza della fotocorrente dalla corrente di massima potenza nelle celle solari quando sono contemporaneamente presenti le resistenze serie e di shunt. Su tale dipendenza influisce molto la resistenza serie. Tuttavia, se questa è dell'ordine di 3 Ω, è ϖI _g/ϖI _mp=1. Si studia anche l'influenza di rivestimenti antiriflettenti di TiO_x sulla tensione di circuito aperto, sulla corrente di circuito aperto e sulla corrente di corto circuito nelle celle di silicio.

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Electrical degradation of porous and dense LSM/YSZ interface

Electrochemical cells formed by the interface between dense and porous lanthanum strontium manganate (LSM) and yttria stabilized zirconia (YSZ) were submitted to annealing temperatures varying from 1373 K to 1673 K for 200 h and studied by Impedance Spectroscopy (IS) in order to investigate how the high annealing temperature can modify the contact between LSM/YSZ and to which extension these changes influence the electrical behavior of dense and porous LSM electrodes before and after the formation of insulating phases. Up to 1473 K the annealing process did not lead to substantial electrical behavior modifications at the LSM/YSZ interfaces for both porous and dense electrodes. IS measurements show two capacitive semicircles, the best fitting of impedance data brings to an equivalent circuit constituted by a serial combination of the electrolyte resistance and two parallel combinations of a resistance and a constant phase element, CPE. The higher frequency semicircles, HF, were attributed to the diffusion of oxide ions from the interface LSM/YSZ to the oxide ion vacancies located at the electrolyte surface. The semicircle at lower frequency, LF, will be ascribed to the oxygen species adsorption and diffusion in the LSM. At 1473 K the only changes recorded are related with the sinterization process of the porous electrodes. Over of 1473 K, the resistance contributions increased largely, especially for porous electrodes, and one additional semicircle was observed. This semicircle was associated to the oxygen diffusion process at the new insulating phases formed from YSZ and LSM solid state reactions. Porous and dense electrodes exhibited different rates for the degradation process. The porous electrode degraded faster than the dense one, probably because of the morphological effects as grain growth and their coalescence during annealing at higher temperatures.     

A mechanistic study on the activation process of (La,Sr)MnO3 electrodes of solid oxide fuel cells

The mechanism of the activation process for the O₂ reduction on (La_0.8Sr_0.2)_0.9MnO₃ (LSM) electrodes is investigated by examining the electrochemical behavior of LSM under cathodic and anodic polarization conditions and the relaxation behavior of LSM under open circuit. A comparative study is also performed on a LSM electrode after dilute acid etching treatment. It has been shown that the segregated SrO has a significant inhibiting effect on the surface exchange process such as dissociative adsorption, incorporation and diffusion of oxygen species on the LSM surface, resulting in the initially very high impedance for the O₂ reduction on LSM electrodes. A mechanism involving the incorporation of SrO into LSM lattice with the concomitant removal of cation vacancies is proposed for the activation effect of cathodic current passage/polarization in solid oxide fuel cells.     

Pinning of pancake vortices in a three-dimensional Josephson medium and structure of the vortex lattice in the “critical” state

A system of pancake vortices formed near the boundary of a sample in a monotonically increasing external magnetic field is calculated with allowance for pinning due to the cellular structure of the medium for various values of the pinning parameter I, which is proportional to the critical current of the junction and the cell diameter. The shortest distance from the outermost vortex to the nearest neighbor is proportional to I ⁻¹¹. It is shown that the pinning parameter has a critical value I _c separating two regimes with different types of critical states. For I<I _c the external magnetic field has a threshold value H _t(I), above which the field immediately penetrates the interior of the junction to an infinite distance. For I>I _c the magnetic field decays linearly from the boundary into the interior of the junction. The value obtained in the study, I _c=3.369, differs from the value of 0.9716 postulated by other authors. The dependence of the slope of the magnetic field profile near the boundary on I is determined. It is shown that the slope is independent of I in intervals 2πk<I<2πk+π. Fiz. Tverd. Tela (St. Petersburg) 39, 1958–1963 (November 1997)     

Characteristic features of the formation of the resistive state in a Bi2Sr2CaCu2Oy crystal

The effect of a magnetic field H⊥(ab) on the transverse current-voltage characteristics (IVCs) of the mixed state of a single crystal of the layered superconductor Bi₂Sr₂CaCu₂O_y (BSCCO) is investigated. It is established that in a wide range of temperatures and fields above the irreversibility line the initial part of the IVC is described by the law V∝I ^γ with γ≃1. As the current increases further, this law is replaced by a section where V∝exp(I). It is established that the multivalued, multibranch characteristics, interpreted as a manifestation of an internal Josephson effect, do not change appreciably when the crystal passes into a state with nonzero linear resistance. The character of the dependence of the characteristic switching current on the first resistive branch, I _J (H,T), is determined. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 8, 543–548 (25 October 1999)