Thermal cycle stability of Al2O3-based compressive seals for planar intermediate temperature solid oxide fuel cells

Al₂O₃-based compressive seals were fabricated by tape casting with Al₂O₃ and 0-30 wt% aluminum powders, and their sealing effectiveness, thermal cycle stability between 200 and 750 °C and applicability in planar intermediate temperature solid oxide fuel cells were evaluated. The results indicate that increasing the aluminum content from 0 to 30 wt% in the seals decreases the leakage rate and increases the thermal cycle stability under various inlet gas (N₂) pressures of 3.5, 7.0 and 10.5 kPa. Especially, with the seal containing 30 wt% of aluminum (ACS3), the initial leakage rate was below 0.03 sccm cm⁻¹ under an inlet pressure of 10.5 kPa, and the leakage rates during 96 thermal cycles were below 0.04 sccm cm⁻¹ under the same inlet gas pressure. The interfaces in the interconnect/seal/cell assembly with the ACS3 seal retained integrity after 50 thermal cycles, demonstrating the applicability of the Al₂O₃-based compressive seals in the planar intermediate temperature SOFCs.     

Hydrogen permeation on Al2O3-based nickel/cobalt composite membranes

Al₂O₃ was synthesized using the sol-gel process with aluminum isopropoxide as the precursor and primary distilled water as the solvent. Nickel and cobalt metal powders were used to increase the strength of the membranes. The Al₂O₃-based membranes were prepared using HPS following a mechanical alloying process. The phase transformation, thermal evolution, surface and cross-section morphology of Al₂O₃ and Al₂O₃-based membranes were characterized by XRD, TG-DTA and FE-SEM. The hydrogen permeation of Al₂O₃-based membranes was examined at 300–473 K under increasing pressure. Hydrogen permeation flux through an Al₂O₃-20wt%Co membrane was obtained to 2.36 mol m⁻² s⁻¹. Reaction enthalpy was calculated to 4.5 kJ/mol using a Van’t Hoff’s plot.     

Optical properties and thermal stability of pulsed-sputter-deposited AlxOy/Al/AlxOy multilayer absorber coatings

Spectrally selective Al_xO_y/Al/Al_xO_y multilayer absorber coatings were deposited on copper (Cu) and molybdenum (Mo) substrates using a pulsed sputtering system. The Al targets were sputtered using asymmetric bipolar-pulsed DC generators in Ar+O₂ and Ar plasmas to deposit an Al_xO_y/Al/Al_xO_y coating. The compositions and thicknesses of the individual component layers were optimized to achieve high solar absorptance (α=0.950-0.970) and low thermal emittance (ε=0.05-0.08). The X-ray diffraction data in thin film mode showed an amorphous structure of the Al_xO_y/Al/Al_xO_y coating. The X-ray photoelectron spectroscopy data of the Al_xO_y/Al/Al_xO_y multilayer absorber indicated that the Al_xO_y layers present in the coating were non-stoichiometric. The optical constants (n and k) of the multilayer absorber were determined from the spectroscopic ellipsometric data. Drude's free-electron model was used for generating the theoretical dispersion of optical constants for Al films, while the Tauc-Lorentz model was used for modeling optical properties of the dielectric Al_xO_y layers. In order to study the thermal stability of the Al_xO_y/Al/Al_xO_y coatings, they were subjected to heat treatment (in air and vacuum) at different temperatures and durations. The multilayer absorber deposited on Cu substrates exhibited high solar selectivity (α/ε) of 0.901/0.06 even after heat-treatment in air up to 400 °C for 2 h. At 450 °C, the solar selectivity decreased significantly on Cu substrates (e.g., α/ε=0.790/0.07). The coatings deposited on Mo substrates were thermally stable up to 800 °C in vacuum with a solar selectivity of 0.934/0.05. The structural stability of the absorber coatings heat treated in air (up to 400 °C) and vacuum (up to 800 °C) was confirmed by micro-Raman spectroscopy measurements. Studies on the accelerated aging tests suggested that the absorber coatings on Cu were stable in air up to 75 h at 300 °C and the service lifetime of the multilayer absorber was predicted to be more than 25 years. Further, the activation energy for the degradation of the multilayer absorber heat treated for longer durations in air is of the order of 64 kJ/mol.     

Electrochemical performance of (Ba0.5Sr0.5)0.9Sm0.1Co0.8Fe0.2O3−δ as an intermediate temperature solid oxide fuel cell cathode

This study presents the electrochemical performance of (Ba_0.5Sr_0.5)_0.9Sm_0.1Co_0.8Fe_0.2O_3−δ (BSSCF) as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC). AC-impedance analyses were carried on an electrolyte supported BSSCF/Sm_0.2Ce_0.8O_1.9 (SDC)/Ag half-cell and a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCF)/SDC/Ag half-cell. In contrast to the BSCF cathode half-cell, the total resistance of the BSSCF cathode half-cell was lower, e.g., at 550 °C; the values for the BSSCF and BSCF were 1.54 and 2.33 Ω cm², respectively. The cell performance measurements were conducted on a Ni-SDC anode supported single cell using a SDC thin film as electrolyte, and BSSCF layer as cathode. The maximum power densities were 681 mW cm⁻² at 600 °C and 820 mW cm⁻² at 650 °C.     

In situ high temperature neutron powder diffraction study of La2Ni0.6Cu0.4O4+δ in air: Correlation with the electrical behaviour

The knowledge of the thermal evolution of the crystal structure of a cathode material across the usual working conditions in solid oxide fuel cells is essential to understand not only its transport properties but also its chemical and mechanical stability in the working environment. In this regard, high-resolution neutron powder diffraction (NPD) measurements have been performed in air from 25 to 900 °C on O₂-treated (350 °C/200 bar) La₂Ni_0.6Cu_0.4O_4+δ. The crystal structure was Rietveld-refined in the tetragonal F4/mmm space group along all the temperature range. The structural data have been correlated with the transport properties of this layered perovskite. The electrical conductivity of O₂-treated La₂Ni_0.6Cu_0.4O_4+δ exhibits a metal (high T)-to-semiconductor (low T) transition as a function of temperature, displaying a maximum value of 110 S cm⁻¹ at around 450 °C. The largest conductivity corresponds, microscopically, to the shortest axial Ni–O2 distance (2.29(1) Å), revealing a major anisotropic component for the electronic transport. We have also performed a durability test at 750 °C for 560 h obtaining a very stable value for the electrical conductivity of 87 S cm⁻¹. The thermal expansion coefficient was 12.8 × 10⁻⁶ K⁻¹ very close to that of the usual SOFC electrolytes. These results exhibit La₂Ni_0.6Cu_0.4O_4+δ as a possible alternative cathode for IT-SOFC.     

Effect of Al2O3 content on the adsorptive properties of Cu/ZnO/Al2O3 for removal of odorant sulfur compounds

Cu/ZnO/Al₂O₃ adsorbents for removal of odorant sulfur compounds were prepared with various Al/Cu molar ratios by co-precipitation method. The sulfur removing ability as a function of Al/Cu molar ratio of the adsorbents for t-butyl mercaptan (TBM), tetrahydro thiophene (THT), dimethyl disulfide (DMS) and H₂S were investigated at 250 °C and 6000 h⁻¹ space velocity. Based on the results of adsorption capacity and characterization by various techniques, the optimum Al/Cu ratio for maximum sulfur removal capacity is found to be at Al/Cu molar ratio of 0.15 which possesses the well-dispersed Cu species with high reducibility. The adsorption capacity is highest for H₂S followed by TBM, DMS and THT. The main role of Al₂O₃ component is to provide the dispersion of CuO species homogeneously with small particle formation and high reducibility.     

Development of Al2O3/glass-based multi-layer composite seals for planar intermediate-temperature solid oxide fuel cells

In this paper, the novel multi-layer composite seals for planar solid oxide fuel cells are studied. The composite seals with sandwiched structure include Al₂O₃-based tape as support and glass-ceramic slurry as binder connecting the interface of the neighboring components. The result finds out that glass-ceramic slurry with 20 wt% Al₂O₃ has the suitable strength and deformability. The thermal cycle characteristics are greatly improved by using the multi-layer composite seals, and the corresponding leakage rates are lower than 0.025 sccm cm⁻¹ for 20 thermal cycles at the inlet pressure ranging from 0.5 psi to 2 psi. SEM investigations show a very compact and good adhesion between the neighboring components, which can minimize the leakage paths. Single cell testing is used to examine the performance of the seals. The value of open circuit voltage is 1.17 V. At the constant discharge current density of 0.37 A cm⁻², the voltage is stabilized at about 0.85 V for 50 h. The results demonstrate that the novel multi-layer composite seals are good candidate for SOFC application.     

SmBaCo2O5+x double-perovskite structure cathode material for intermediate-temperature solid-oxide fuel cells

SmBaCo₂O_5+x (SBCO), an oxide with double-perovskite structure, has been developed as a novel cathode material for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The electrical conductivity of an SBCO sample reaches 815–434 S cm⁻¹ in the temperature range 500–800 °C. XRD results show that an SBCO cathode is chemically compatible with the intermediate-temperature electrolyte materials Sm_0.2Ce_0.8O_1.9 (SDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM). The polarization resistances of an SBCO cathode on SDC and LSGM electrolytes are 0.098 and 0.054 Ω cm² at 750 °C, respectively. The maximum power densities of a single cell with an SBCO cathode on SDC and LSGM electrolytes reach 641 and 777 mW cm⁻² at 800 °C, respectively. The results of this study demonstrate that the double-perovskite structure oxide SBCO is a very promising cathode material for use in IT-SOFCs.     

Development of novel glass-based composite seals for planar intermediate temperature solid oxide fuel cells

Novel glass-based composite seals prepared by tape casting are evaluated as sealing materials in solid oxide fuel cell. The leakage rates are measured at the inlet pressure of 1, 2 and 3 psi under different compressive stresses and temperatures respectively. The results show that all of measured leakage rates are lower than 0.01 sccm cm⁻¹ and increase with higher inlet pressure and lower test temperatures. The leakage rates during thermal cycling are conducted under a compressive stress of 20 psi at 750 °C, which indicate excellent thermal cycle stability of the seals. Good compatibility between seals and the adjacent components provide well interface contact which could avoid the formation of leakage paths. When the seal is applied for single cell testing, the open circuit voltage of 1.13 V and undetectable degradation clearly demonstrate the applicable performance of glass-based composite seal in solid oxide fuel cell.     

Electrochemical performance of a solid oxide fuel cell based on Ce0.8Sm0.2O2−δ electrolyte synthesized by a polymer assisted combustion method

A polyvinyl alcohol assisted combustion synthesis method was used to prepare Ce_0.8Sm_0.2O_2−δ (SDC) powders for an intermediate temperature solid oxide fuel cell (IT-SOFC). The XRD results showed that this combustion synthesis route could yield phase-pure SDC powders at a relatively low calcination temperature. A thin SDC electrolyte film with thickness control was produced by a dry pressing method at a lower sintering temperature of 1250 °C. With Sm_0.5Sr_0.5Co₃-SDC as the composite cathode, a single cell based on this thin SDC electrolyte was tested from 550 to 650 °C. The maximum power density of 936 mW cm⁻² was achieved at 650 °C using humidified hydrogen as the fuel and stationary air as the oxidant.     

Study on Sm1.8Ce0.2CuO4-Ce0.9Gd0.1O1.95 composite cathode materials for intermediate temperature solid oxide fuel cell

Sm_1.8Ce_0.2CuO₄-xCe_0.9Gd_0.1O_1.95 (SCC-xCGO, x = 0-12 vol.%) composite cathodes supported on Ce_0.9Gd_0.1O_1.95 (CGO) electrolyte are studied for applications in IT-SOFCs. Results show that Sm_1.8Ce_0.2CuO₄ material is chemically compatible with Ce_0.9Gd_0.1O_1.95 at 1000 °C. The composite electrode exhibits optimum microstructure and forms good contact with the electrolyte after sintering at 1000 °C for 4 h. The polarization resistance (R_p) reduces to the minimum value of 0.17 Ω cm² at 750 °C in air for SCC-CGO06 composite cathode. The relationship between R_p and oxygen partial pressure indicates that the reaction rate-limiting step is the surface diffusion of the dissociative adsorbed oxygen on the composite cathode.     

Co-doped Sr2FeNbO6 as cathode materials for intermediate-temperature solid oxide fuel cells

Sr₂Fe_1−xCo_xNbO₆ (0.1 ≤ x ≤ 0.9) (SFCN) oxides with perovskite structure have been developed as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). These materials are synthesized via solid-state reaction and characterized by XRD, SEM, electrical conductivity, AC impedance spectroscopy and DC polarization measurements. The reactivity tests show that the Sr₂Fe_1−xCo_xNbO₆ electrodes are chemically compatible with the Zr_0.85Y_0.15O_1.925 (YSZ) and Ce_1.9Gd_0.1O_1.95 (CGO) electrolytes at 1200 °C, and the electrode forms a good contact with the electrolyte after sintering at 1200 °C for 12 h. The total electrical conductivity that has a considerable effect on the electrode properties is determined in a temperature range from 200 °C to 800 °C. The highest conductivity of 5.7 S cm⁻¹ is found for Sr₂Fe_0.1Co_0.9NbO₆ at 800 °C in air. The electrochemical performances of these cathode materials are studied using impedance spectroscopy at various temperatures and oxygen partial pressures. Two different kinds of reaction rate-limiting steps exist on the Sr₂Fe_0.1Co_0.9NbO₆ electrode, depending on the temperature. The Sr₂Fe_0.1Co_0.9NbO₆ electrode on CGO electrolyte exhibits a polarization resistance of 0.74 Ω cm² at 750 °C in air, which indicates that the Sr₂Fe_0.1Co_0.9NbO₆ electrode is a promising cathode material for IT-SOFCs.     

Investigation on silver electric adhesive doped with Al2O3 ceramic particles for sealing planar solid oxide fuel cell

The silver electric adhesive doped with Al₂O₃ ceramic particles is used as sealing material for planar solid oxide fuel cell (SOFC). The sealing temperature of this sealing material is 600 °C with the heating rate of 2 °C min⁻¹, and the minimal leak rate ranges from 0.030 sccm cm⁻¹ to 0.040 sccm cm⁻¹. When doping 15 mass% Al₂O₃ ceramic particles into this sealing material, the thermal expansion coefficient of this material decreases from 20 ppm K⁻¹ to 15 ppm K⁻¹, which improves the thermal matching performance and the long-term stability of the material significantly. When using the gradient sealing method with the pure silver electric adhesive and the silver electric adhesive doped with Al₂O₃ ceramic particles to seal the interface of Ni-YSZ/SUS430 in the simulating cell, the minimal leak rate of 0.035 sccm cm⁻¹ is obtained for the cell. Furthermore, the simulating cell sealed with the compound silver electric adhesive presents good heat-resistant impact ability. Therefore, this compound sealing technique is a very promising sealing method for SOFC.     

Preparation of supported SrCeO3-based membrane by spin coating method

SrCe_0.9Y_0.1O_3−δ (SCY10) powder with a pure perovskite phase is prepared by solid-state reaction method. NiO is dispersed uniformly in SCY10 powder to fabricate NiO-SCY10 anode substrate. The starting powder, the mixture of SrCO₃, CeO₂ and Y₂O₃, is deposited directly on the green substrate instead of SCY10 powder by spin coating. After co-firing at 1300 °C for 3 h, the starting powder reacts to form SCY10 top layer on the substrate. SEM micrographs show that the top layer is defect-free and adheres well with the anode substrate without any delamination. A single fuel cell is assembled with anode-supported SCY10 membrane as electrolyte membrane and Ag as cathode. The electrochemical property of the fuel cell is tested with hydrogen as fuel in the temperature range of 600-800 °C. The open circuit voltage (OCV) reaches 1.05 V at 800 °C, and the maximum power density is 50 mW cm⁻², 155 mW cm⁻², 200 mW cm⁻² at 600 °C, 700 °C, 800 °C, respectively.     

LiCr0.2Ni0.4Mn1.4O4 spinels exhibiting huge rate capability at 25 and 55 °C: Analysis of the effect of the particle size

The comparison of the rate capability of LiCr_0.2Ni_0.4Mn_1.4O₄ spinels synthesized by the sucrose aided combustion method at 900, 950 and 1000 °C is presented. XRD and TEM studies show that the spinel cubic structure remains unchanged on heating but the particle size is notably modified. Indeed, it increases from 695 nm at 900 °C to 1465 nm at 1000 °C. The electrochemical properties have been evaluated by galvanostatic cycling at 25 and 55 °C between 1 C and 60 C discharge rates. At both temperatures, all samples exhibit high working voltage (∼4.7 V), elevated capacity (∼140 mAh g⁻¹) and high cyclability (capacity retention ∼99% after 50 cycles even at 55 °C). The samples also have huge rate capability. They retain more than 70% of their maximum capacity at the very fast rate of 60 C. The effect of the particle size on the rate capability at 25 and at 55 °C has been investigated. It was demonstrated that LiCr_0.2Ni_0.4Mn_1.4O₄ annealed at 900 °C, with the lowest particle size, has the best electrochemical performances. In fact, among the LiNi_0.5Mn_1.5O₄-based cathodes, SAC900 exhibits the highest rate capability ever published. This spinel, able to deliver 31,000 W kg⁻¹ at 25 °C and 27,500 W kg⁻¹ at 55 °C is a really promising cathode for high-power Li-ion battery.     

NiMn2O4 spinel as an alternative coating material for metallic interconnects of intermediate temperature solid oxide fuel cells

In an effort to improve the performance of SUS 430 alloy as a metallic interconnect material, a low cost and Cr-free spinel coating of NiMn₂O₄ is prepared on SUS 430 alloy substrate by the sol-gel method and evaluated in terms of the microstructure, oxidation resistance and electrical conductivity. A oxide scale of 3-4 μm thick is formed during cyclic oxidation at 750 °C in air for 1000 h, consisting of an inner layer of doped Cr₂O₃ and an outer layer of doped NiMn₂O₄ and Mn₂O₃; and the growth of Cr₂O₃ and formation of MnCr₂O₄ are depressed. The oxidation kinetics obeys the parabolic law with a rate constant as low as 4.59 × 10⁻¹⁵ g² cm⁻⁴ s⁻¹. The area specific resistance at temperatures between 600 and 800 °C is in the range of 6 and 17 mΩ cm². The above results indicate that NiMn₂O₄ is a promising coating material for metallic interconnects of the intermediate temperature solid oxide fuel cells.     

Al-doped Li7La3Zr2O12 synthesized by a polymerized complex method

Li₇La₃Zr₂O₁₂ electrolytes doped with different amounts of Al (0, 0.2, 0.7, 1.2, and 2.5 wt.%) were prepared by a polymerized complex (Pechini) method. The influence of aluminum on the structure and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X-ray diffraction (XRD), impedance spectroscopy, scanning electron microscopy (SEM), and thermal dilatometry. It was found that even a small amount of Al (e.g. 0.2 wt.%) added to Li₇La₃Zr₂O₁₂ can greatly accelerate densification during the sintering process. SEM micrographs showed the existence of a liquid phase introduced by Al additions which led to the enhanced sintering rate. The addition of Al also stabilized the higher conductivity cubic form of Li₇La₃Zr₂O₁₂ rather than the less conductive tetragonal form. The combination of these two beneficial effects of Al enabled greatly reduced sintering times for preparation of highly conductive Li₇La₃Zr₂O₁₂ electrolyte. With optimal additions of Al (e.g. 1.2 wt.%), Li₇La₃Zr₂O₁₂ electrolyte sintered at 1200 °C for only 6 h showed an ionic conductivity of 2.0 × 10⁻⁴ S cm⁻¹ at room temperature.     

Fabrication and characterization of a co-fired La0.6Sr0.4Co0.2Fe0.8O3−δ cathode-supported Ce0.9Gd0.1O1.95 thin-film for IT-SOFCs

A dense membrane of Ce_0.9Gd_0.1O_1.95 on a porous cathode based on a mixed conducting La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ was fabricated via a slurry coating/co-firing process. With the purpose of matching of shrinkage between the support cathode and the supported membrane, nano-Ce_0.9Gd_0.1O_1.95 powder with specific surface area of 30 m² g⁻¹ was synthesized by a newly devised coprecipitation to make the low-temperature sinterable electrolyte, whereas 39 m² g⁻¹ nano-Ce_0.9Gd_0.1O_1.95 prepared from citrate method was added to the cathode to favor the shrinkage for the La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ. Bi-layers consisting of <20 μm dense ceria film on 2 mm thick porous cathode were successfully fabricated at 1200 °C. This was followed by co-firing with NiO–Ce_0.9Gd_0.1O_1.95 at 1100 °C to form a thin, porous, and well-adherent anode. The laboratory-sized cathode-supported cell was shown to operate below 600 °C, and the maximum power density obtained was 35 mW cm⁻² at 550 °C, 60 mW cm⁻² at 600 °C.     

Combustion synthesis and properties of highly phase-pure perovskite electrolyte Co-doped La0.9Sr0.1Ga0.8Mg0.2O2.85 for IT-SOFCs

The highly phase-pure perovskite electrolyte, La_0.9Sr_0.1Ga_0.8Mg_0.115Co_0.085O_2.85 (LSGMCO), was prepared by means of glycine–nitrate process (GNP) for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The perovskite phase evolution, sintering, electrical conductivity and electrochemical performance of LSGMCO were investigated. The results show that the highly phase-pure perovskite electrolyte LSGMCO can be obtained after calcining at 1150 °C. The sample sintered at 1450 °C for 20 h in air exhibited a better sinterability, and the relative density of LSGMCO was higher than 95%. The stoichiometric indexes of the elements in the sintered sample LSGMCO determined experimentally by EDS were in good agreement with the nominal composition. The electrical conductivities of the sample were 0.094 and 0.124 S· cm⁻¹ at 800 °C and 850 °C in air, respectively. The ionic conduction of the sample was dominant at high temperature with the higher activation energies. While at lower temperature the electron hole conduction was predominated with the lower activation energies. The maximum power densities of the single cell fabricated with LSGMCO electrolyte with Ce_0.8Sm_0.2O_1.9 (SDC) interlayer, SmBaCo₂O_5+x cathode and NiO/SDC anode achieved 643 and 802 mW cm⁻² at 800 °C and 850 °C, respectively.     

Long-term ageing and materials degradation of hybrid mica compressive seals for solid oxide fuel cells

Hybrid phlogopite mica seals with silver interlayers were evaluated in long-term isothermal ageing tests in a dual environment consisting of dilute hydrogen versus air at 800 °C. High-temperature leak tests with helium showed very stable leakage of 0.01-0.02 sccm cm⁻¹ for 28,366 h under a low applied compressive stress of 82 kPa (12 psi). Post-mortem SEM and EDS analyses of the mica showed minimum degradation in terms of changes in microstructure and chemical composition, although there appeared to be some Ag migration and segregation at interstices between mica flakes. Fluorine was also found to be released from mica. Overall, the low, constant leakage through the hybrid mica/Ag seals clearly demonstrated a very promising candidate for SOFC sealing.