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.     

Correlation between microstructure and degradation in conductivity for cubic Y2O3-doped ZrO2

The application of Yttria-stabilized Zirconia (YSZ) as solid electrolyte in high-temperature solid oxide fuel cells (SOFC) is well established. However, the strong decrease of the ionic conductivity in 8.5 mol% Y₂O₃-doped ZrO₂ at high temperature has not yet been clarified completely. To contribute to the understanding of the degradation process, transmission electron microscopy (TEM) was applied to analyze the microstructure in YSZ electrolyte substrates in as-sintered and aged material. Selected area electron diffraction and conventional TEM imaging were performed to investigate the evolution of different phases and phase transitions in YSZ. Grain boundary charging and the possible formation of a glassy phase at grain boundaries after aging were investigated using transmission electron holography and high-resolution TEM. The ionic conductivity was characterized by dc-conductivity measurements and impedance spectroscopy.     

Preparation of thin film SOFCs working at reduced temperature

SOFCs are expected to become competitive devices for electrical power generation, but successful application is dependent on decreasing working temperature from 1000 to 800 °C, without detrimental effects on resistance and on electrode processes. This requires a reduction of the stabilised zirconia electrolyte thickness and an optimisation of the electrodes and interfaces. We have studied the preparation of a thin film SOFC device working at intermediate temperatures (less than 850 °C). The electrolyte must be very dense and as thin as possible to avoid ohmic losses. Electrodes, anode and cathode, must be porous enough to enable the gas fluxes to go through. Ni/YSZ cermet anodes have been prepared by a conventional ceramic method and support the cells. Thin Yttria Stabilised Zirconia electrolytes (YSZ) have been deposited by RF sputtering, DC sputtering and spray pyrolysis onto a Ni/YSZ cermet. Thin film La_0.7Sr_0.3MnO₃ (LSM) cathodes have been deposited onto the electrolytes by a spray-pyrolysis method. We present here the preparation and the characterisation of each component and the electrochemical performance of such cells at 850 °C. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

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.     

Electrical properties of thin yttria-stabilized zirconia overlayers produced by atomic layer deposition for solid oxide fuel cell applications

Thin films of yttria-stabilized zirconia (YSZ) electrolyte were prepared by atomic layer deposition at 300 °C for solid oxide fuel cell (SOFC) applications. YSZ samples of 300-1000 nm thickness were deposited onto La_0.8Sr_0.2MnO₃ (LSM) cathodes. A microstructural study was performed on these samples and their electrical properties were characterised between 100 and 390 °C by impedance spectroscopy. A remarkable feature is that the as-deposited layers were already crystalline without any annealing treatment. Their resistance decreased when reducing the layer thickness; nevertheless, their conductivity and activation energy were significantly lower than those reported in the literature for bulk YSZ.     

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.     

Fabrication and electrochemical performance of La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> impregnated porous YSZ cathode

La_0.5Sr_0.5CoO₃-yttria-stabilized zirconia (LSCO-YSZ) composite cathode for solid oxide fuel cell (SOFC) has been fabricated by wet impregnation method. Nitrate precursors of La, Sr, and Co have been impregnated into the pre-sintered porous YSZ matrix, which is converted into LSCO phase after calcination at 850 °C in the presence of glycine as confirmed from X-ray diffraction. LSCO of 5, 7, and 10 wt% impregnated porous YSZ have been electrochemically characterized using 2-probe AC conductivity method. Maximum ionic conductivity of 0.27 S/cm at 800 °C and activation energy of 0.15 eV between 600 and 800 °C have been observed for 10 wt% LSCO-YSZ cathode. Area-specific resistance of 1.01 Ω cm² at 800 °C is estimated for the electrolyte-supported half-cell (10 wt% LSCO-YSZ/YSZ). After testing the LSCO-YSZ cathode matrix, the electrolyte-supported full cell (10 wt% LSCO-YSZ/YSZ/NiO-YSZ) has been tested and produced maximum power density 51.12 mW/cm² (109.38 mA/cm²) at 800 °C. The electrolyte-supported full cell exhibited 6 Ω cm² electrode polarization at 800 °C in H₂, which is in higher side leading to low performance. LSCO-YSZ/YSZ/NiO-YSZ SOFC found to give stable performance up to 2 h and scanning electron microscopy analysis has been carried out before and after cell testing to assess the morphological changes.     

Reactivity and diffusion between La0.8Sr0.2MnO3 and ZrO2 at interfaces in SOFC cores by TEM analyses on FIB samples

In this paper, we investigate the diffusion and reactivity at the interface between the electrolyte (YSZ) and the cathode (LSM) of planar SOFC single cells by Analytical and High Resolution Transmission Microscopy. Cells were obtained via an aqueous tape-casting process allowing casting the three layers (cathode, electrolyte, anode [Ni-YSZ]) in a single operation. To allow the cell to function at intermediate temperatures (750–850 °C), the final electrolyte thickness after co-sintering at 1350 °C must range between 40 μm and 50 μm. As-sintered cells as well as cells that have been operated at 850 °C have been considered here; it is shown that the electrical performances were one order of magnitude less than expected and that they deteriorated quickly under operating conditions.In order to explain this behavior, we carried out analytical transmission electron microcopy. To obtain precisely located chemical and structural information, we used the “H-Shape” as well as the Lift Out FIB (Focused Ion Beam) techniques to extract 5 × 10 × 0.1 μm TEM samples; additional High Resolution characterization was carried out at interfaces between LSM and YSZ grains on standard ion-milled samples. We showed that the co-sintering temperature (1350 °C) was responsible for some diffusion of manganese through the electrolyte and the cathode, leading then to the rise of a significant electronic conduction and to the drop off of the ionic conductivity, and accounts for the germination and growth of the resistive pyrochlore phase La₂Zr₂O₇. Operating the cell at 850 °C do not aggravate these phenomena, but rather alters the anode microstructure.     

Processing and characterization of ultra-thin yttria-stabilized zirconia (YSZ) electrolytic films for SOFC

Sub-micron yttria-stabilized zirconia (YSZ) electrolyte layer was prepared by a liquid state deposition method and with an average thickness of 0.5 μm to improve the performance of the anode-supported solid oxide fuel cell (SOFC). The YSZ precursors, containing yttrium and zirconium species and an additive, poly-vinyl-pyrrolidone (PVP), were spin-coated on a Ni/YSZ anode substrate. Several properties, including crystalline phases, microstructures, and current–voltage (I–V) characteristics, were investigated. The thin film of 4 mol% Y₂O₃-doped ZrO₂ (4YSZ) consisted of cubic, tetragonal, and a trace of monoclinic phases, and showed a crack-free layer after sintering at 1300 °C. The anode supported SOFC, which consists of the Ni–YSZ anode, 4YSZ electrolyte, and Pt/Pd cathode, showed power densities of 477 mW/cm² at 600 °C, and 684 mW/cm² at 800 °C. Otherwise, the surface cracks of the other YSZ-coated samples (e.g. 8YSZ) can be repaired by a multi-coating method.     

Influence of YSZ electrolyte thickness on the characteristics of plasma-sprayed cermet supported tubular SOFC

Novel Ni–Al₂O₃ cermet-supported tubular SOFC cell was fabricated by thermal spraying. Flame-sprayed Al₂O₃–Ni cermet coating played dual roles of a support tube and an anode current collector. Y₂O₃-stabilized ZrO₂ (YSZ) electrolyte was deposited by atmospheric plasma spraying (APS) to aim at reducing manufacturing cost. The gas tightness of APS YSZ coating was achieved by post-densification process. The influence of YSZ coating thickness on the performance of SOFC test cell was investigated in order to optimize YSZ thickness in terms of open circuit voltage of the cell and YSZ ohmic loss. It was found that the reduction of YSZ thickness from 100 μm to 40 μm led to the increase of the maximum output power density from 0.47 W/cm² to 0.76 W/cm² at 1000 °C. Using an APS 4.5YSZ coating of about 40 μm as the electrolyte, the test cell presented a maximum power output density of over 0.88 W/cm² at 1030 °C. The results indicate that SOFCs with thin YSZ electrolyte require more effective cathode and anode to improve performance.     

Investigation of chemisorbed oxygen, surface segregation and effect of post-treatments on La0.8Sr0.2MnO3 powder and screen-printed layers for solid oxide fuel cell cathodes

In order to better understand the mechanism of the reaction of oxygen reduction at the surface of strontium doped lanthanum manganites (LSM) cathodes in solid electrolyte fuel cells (SOFC), the surface properties of La_0.8Sr_0.2MnO₃ powders and screen-printed layers have been characterised by various techniques.Strontium enrichment at the surface has been evidenced by X-ray photoelectron spectroscopy according to the conditions of annealing (temperature, oxygen pressure) and polarisation treatments of the samples.The interaction between oxygen and La_0.8Sr_0.2MnO₃ for SOFC cathodes has been studied by thermo-programmed desorption, in situ infrared spectrometry and calorimetry. The results indicate that various adsorbed oxygen species may exist on the surface of LSM depending on temperature.The presence of various adsorbed oxygen species and the surface Sr segregation are important factors to consider in the mechanism of oxygen reduction at LSM SOFC cathodes since they could be responsible for many discrepancies between the interpretations that can be found in the literature data.     

Effect of alumina additions in YSZ on the microstructure and degradation of the LSM–YSZ interface

The cathode–electrolyte interface in a solid oxide fuel cell is examined to understand why premature delamination is observed in alumina substituted YSZ electrolyte. From XRD, SEM and TEM observations it was concluded that after high temperature sintering a tetragonal (Mn,Al)₃O₄ forms at the interface, which during prolonged fuel cell operation forms a cubic (Mn,Al)₃O₄ phase. This transformation is associated with volume decrease creating voids which ultimately weaken the cathode–electrolyte interface sufficiently for the cathode layer to delaminate off the YSZ–Al₂O₃ electrolyte.     

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.     

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.     

CeO<Subscript>2</Subscript> and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> modified Ni-YSZ anode for solid oxide fuel cell

Ni sintering at high temperature (～ 800 °C) operation drastically degrades the performance of Ni-yttria-stabilized zirconia (YSZ) anode in solid oxide fuel cell (SOFC). Mixed ionic and electronic conductive oxides such as CeO₂ and Nb₂O₅ enhance the dispersion of Ni, CeO₂ enhances the redox behavior and promotes charge transfer reactions, and Nb₂O₅ increases the triple phase boundary. In the present work, anode-supported SOFC is fabricated and tested in H₂ fuel at 800 °C. YSZ and lanthanum strontium manganite (LSM)-YSZ are used as the electrolyte and composite cathode with NiO-YSZ, CeO₂-NiO-YSZ, and Nb₂O₅-NiO-YSZ as an anode. The peak power density obtained for the cell with 10% CeO₂–30% NiO-YSZ anode at the 5 and 25 h of operation is 330 and 290 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). The peak power density obtained for the cell with 10% Nb₂O₅–30% NiO-YSZ anode at the 5 and 25 h of operation is 301 and 285 mW cm^?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm^?2 at 5 h). Physical characterization has been carried to study morphology, elemental analysis, particle size, and phase formation of the fabricated anode before and after cell operation to correlate the cell performance.     

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.     

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.     

Cathode overpotential investigation by means of “Built-in” potential electrode

The objective of the present work is the development of a “built-in” potential electrode method for direct measurements of the cathode and anode overpotentials and the corresponding interface resistances of solid oxide fuel cells (SOFC). The studies were performed on a yttria-stabilised zirconia (YSZ) electrolyte-supported SOFC using La_0.8Sr_0.2MnO₃ as cathode, GDC as protecting layer and Ni-ScSZ cermet as anode. The mesh potential electrode was placed inside the YSZ membrane near the cathode side. Using the combination of the I-U and the impedance measurements with the built-in potential electrode technique, the temperature dependencies of the electrodes and electrolyte contributions to the total cell resistance were determined.     

Electrochemical properties of nanostructured lanthanum strontium manganite cathode fabricated by electrostatic spray deposition

Electrostatic spray deposition was applied to prepare nanoporous lanthanum strontium manganite (LSM) films with high specific surface area (37.34 m²/g) for the cathode application in solid oxide fuel cell (SOFC). The electrochemical characteristics were investigated at a temperature range from 546 to 777 °C and oxygen partial pressure from 0.01 to 1.0 atm. The diffusion of atomic oxygen and oxygen ion transfer from three-phase boundary to the YSZ electrolyte were found to be the rate-determining steps for oxygen reduction reaction on LSM cathode. The polarization resistance of the LSM prepared using electrostatic spray deposition decreased from 15 to 1.2 Ωcm² with increasing temperature from 546 to 777 °C and the activation energy was 0.81 eV. It was demonstrated that the ESD method offers a promising approach for the preparation of electrochemically active nanoporous layers, particularly applicable for solid oxide fuel cells.     

Gadolinia-doped ceria films deposited by RF reactive magnetron sputtering

Gadolinia-doped ceria (GDC) films were prepared by RF reactive magnetron sputtering from a Gd-10 at.% Ce alloy target in reactive O₂/Ar gas mixtures and annealed at 700 °C for 2 h. Material characteristics and chemical compositions of GDC films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Electrical behaviors were measured by AC impedance in the range of 500–700 °C at OCV for air condition. The microstructure of GDC films was found to be an assembly of columnar crystallites with a cubic fluorite structure. The total conductivity of 700 °C-annealed GDC (GDC-1) with the obtained composition of (Ce_0.911Gd_0.089)O_1.938 was higher than that of bulk yttria-stabilized zirconia (YSZ), but smaller than bulk GDC. The governing mechanism of conduction of sputtered-GDC electrolyte films was mainly governed by a grain boundary process, which resulted in a blocking effect and the lower conductivity of thin films than that of bulk GDC samples. Our results suggested that sputtered-GDC films with a comparable conductivity can be used as solid electrolyte layers for a solid oxide fuel cell (SOFC) system as compared to the well-known YSZ.