Characterization of the 75% Gd0.8Sr0.2CoO3−δ/25% Ce0.9Gd0.1O2−δ composite cathode system for use in intermediate temperature solid oxide fuel cells

The composite cathode system is examined for suitability on a Ce_0.9Gd_0.1O_2−δ electrolyte based solid oxide fuel cell at intermediate temperatures (500–700 °C). The cathode is characterized for electronic conductivity and area specific charge transfer resistance. This cathode system is chosen for its excellent thermal expansion match to the electrolyte, its relatively high conductivity (115 S cm⁻¹ at 700 °C), and its low activation energy for oxygen reduction (99 kJ mol⁻¹). It is found that the decrease of sintering temperature of the composite cathode system produces a significant decrease in charge transfer resistances to as low as 0.25 Ω cm². The conductivity of the cathode systems is between 40 and 88 S cm⁻¹ for open porosities of 30–40%.     

Electrical properties of Mg-doped Gd0.1Ce0.9O1.95 under different sintering conditions

Ce_0.9Gd_0.1O_1.95 with various Mg doping contents was synthesized by citric acid-nitrate low temperature combustion process and sintered under different conditions. The crystal structures, microstructures and electrical properties were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and ac impedance spectroscopy. Low solubility of Mg²⁺ in Ce_0.9Gd_0.1O_1.95 lattice was evidenced by XRD and FESEM micrographs. The samples sintered at 1300 °C exhibited the higher total conductivity than those sintered at 1100 and 1500 °C, with the maximum value of 1.48 × 10⁻² S cm⁻¹ (measured at 600 °C) at the Mg doping content of 6 mol%, corresponding to the minimum total activation energy (E_tol) of 0.84 eV (150–400 °C). The effect of Mg doping on the electrical conductivity was significant particularly at higher sintering temperatures. At the sintering temperature of 1500 °C, the addition of Mg (10 mol%) enhanced the grain boundary conductivity by over 10² times comparing with that of undoped Ce_0.9Gd_0.1O_1.95, which may be explained by the optimization of space charge layer due to the segregation of Mg²⁺ to the grain boundaries.     

Characterization of Pr1−xSrxCo0.8Fe0.2O3−δ (0.2 ≤ x ≤ 0.6) cathode materials for intermediate-temperature solid oxide fuel cells

Cathode materials consisting of Pr_1−xSr_xCo_0.8Fe_0.2O_3−δ (x = 0.2–0.6) were prepared by the sol–gel process for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The samples had an orthorhombic perovskite structure. The electrical conductivities were all higher than 279 S cm⁻¹. The highest conductivity, 1040 S cm⁻¹, was found at 300 °C for the composition x = 0.4. Symmetrical cathodes made of Pr_0.6Sr_0.4Co_0.8Fe_0.2O_3−δ (PSCF)–Ce_0.85Gd_0.15O_1.925 (50:50 by weight) composite powders were screen-printed on GDC electrolyte pellets. The area specific resistance value for the PSCF–GDC cathode was as low as 0.046 Ω cm² at 800 °C. The maximum power densities of a cell using the PSCF–GDC cathode were 520 mW cm⁻², 435 mW cm⁻² and 303 mW cm⁻² at 800 °C, 750 °C and 700 °C, respectively.     

High performance of proton-conducting solid oxide fuel cell with a layered PrBaCo2O5+δ cathode

A dense BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) electrolyte is fabricated on a porous anode by in situ drop-coating method which can lead to extremely thin electrolyte membrane (10 μm in thickness). The layered perovskite structure oxide PrBaCo₂O_5+δ (PBCO) is synthesized by auto ignition process and initially examined as a cathode for proton-conducting IT-SOFCs. The electrical conductivity of PrBaCo₂O_5+δ (PBCO) reaches the general required value for the electrical conductivity of cathode absolutely. The single cell, consisting of PrBaCo₂O_5+δ (PBCO)/BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY)/NiO-BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY) structure, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and air as the oxidant. An open-circuit potential of 1.01 V and a maximum power density of 545 mW cm⁻² at 700 °C are obtained for the single cell, and a low polarization resistance of the electrodes of 0.15 Ω cm² is achieved at 700 °C.     

Influence of microstructure and applied current on the electrical conductivity of SmBaCo2O5+d cathode in solid oxide fuel cell

In this study, the electrical conductivity of SmBaCo₂O_5+d (SBCO) is measured and analyzed with respect to the microstructure of the analyzed samples. The microstructure is influenced by the sintering temperature and by the precise composition of the composite cathode. Difference in the electrical conductivity at different applied current is investigated. The value of the electrical conductivity of SBCO sintered at 1150 °C was about 1024 S/cm at 600 °C, which was the highest compared to other samples sintered at lower temperatures. The electrical conductivities of porous microstructural SBCO sintered at 1150 °C with an addition of 10 wt% carbon black and of a composite cathode comprised of SBCO and Ce_0.9Gd_0.1O₂ (CGO91) at a ratio of 1.9:0.1 were 256 and 525 S/cm at 600 °C. The electrical conductivities of SBCO samples increase when relatively low currents are applied. This trend can be observed at all pure SBCO and samples mixed with carbon black. However, these properties are not found in composite cathodes comprised of SBCO and CGO91.     

Preparation of sulfonated poly(ether ether ketone)s containing amino groups/epoxy resin composite membranes and their in situ crosslinking for application in fuel cells

A series of amino-containing sulfonated poly(aryl ether ketone)/4,4′-diglycidyl(biphenyl) epoxy resin (DGBP) composite membranes for proton exchange membranes fuel cells (PEMFCs) are prepared by solution blending and casting. The reaction kinetics and the effects of introduction of DGBP content on the properties of the composite membranes are thoroughly investigated. The crosslinked composite membranes after treatment at either 120 °C or 200 °C have improved oxidative and dimensional stability than those without crosslinking. Despite the fact that crosslinked membranes generally have lower proton conductivity in comparison with the original ones, the proton conductivities of the membranes treated at 120 °C are above 2.22 × 10⁻² S cm⁻¹ at room temperature and 9.42 × 10⁻² S cm⁻¹ at 100 °C. Even for the samples treated at 200 °C, their proton conductivities are still higher than 1.26 × 10⁻² S cm⁻¹ at room temperature and higher than 8.67 × 10⁻² S cm⁻¹ at 100 °C, which are well satisfied with elementary requirement of fuel cells. In addition, all the evaluated membranes have low methanol permeability. For example, the methanol permeability of AP6FSPEEK/DGBP1 cured at 200 °C is 0.33 × 10⁻⁶ cm² s⁻¹, which is an order magnitude lower than Nafion 117. Therefore, these novel crosslinked composite membranes could be potential usage in fuel cells.     

ZnO-doped BaZr0.85Y0.15O3−δ proton-conducting electrolytes: Characterization and fabrication of thin films

ZnO-doped BaZr_0.85Y_0.15O_3−δ perovskite oxide sintered at 1500 °C has bulk conductivity of the order of 10⁻² S cm⁻¹ above 650 °C, which makes it an attractive proton-conducting electrolyte for intermediate-temperature solid oxide fuel cells. The structure, morphology and electrical conductivity of the electrolyte vary with sintering temperature. Optimal electrochemical performance is achieved when the sintering temperature is about 1500 °C. Cathode-supported electrolyte assemblies were prepared using spin coating technique. Thin film electrolytes were shown to be dense using SEM and EDX analyses.     

A high performance intermediate temperature fuel cell based on a thick oxide–carbonate electrolyte

A high performance intermediate temperature fuel cell (ITFC) with composite electrolyte composed of co-doped ceria Ce_0.8Gd_0.05Y_0.15O_1.9 (GYDC) and a binary carbonate-based (52 mol% Li₂CO₃/48 mol% Na₂CO₃), 1.2 mm thick electrolyte layer has been developed. Co-doped Ce_0.8Gd_0.05Y_0.15O_1.9 was synthesized by a glycine–nitrate process and used as solid support matrix for the composite electrolyte. The conductivity of both composite electrolyte and GYDC supporting substrate were measured by AC impedance spectroscopy. It showed a sharp conductivity jump at about 500 °C when the carbonates melted. Single cells with thick electrolyte layer were fabricated by a dry-pressing technique using NiO as anode and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ or lithiated NiO as cathode. The cell was tested at 450–550 °C using hydrogen as the fuel and air as the oxidant. Excellent performance with high power density of 670 mW cm⁻² at 550 °C was achieved for a 1.2 mm thick composite electrolyte containing 40 wt% carbonates which is much higher than that of a cell based on pure GYDC with a 70 μm thick electrolyte layer.     

Reduction of defects of polycrystalline silicon thin films by heat treatment with high-pressure H2O vapor

An improvement of electrical properties of pulsed laser crystalllized silicon films was achieved by simple heat treatment with high-pressure H₂O vapor. The electrical conductivity of 7.4×10¹⁷ cm⁻³ phosphorus-doped 50-nm-thick pulsed laser crystallized silicon films was markedly increased from 1.6×10⁻⁵ S/cm (as crystallized) to 2 S/cm by heat treatment at 270°C for 3 h with 1.25×10⁶ Pa H₂O vapor because of reduction of density of defect states localized at grain boundaries. Spin density was reduced from 1.7×10¹⁸ cm⁻³ (as crystallized) to 1.2×10¹⁷ cm⁻³ by heat treatment at 310°C for 3 h with 1.25×10⁶ Pa H₂O vapor.     

Improved electrochemical performance and thermal compatibility of Fe- and Cu-doped SmBaCo2O5+δ-Ce0.9Gd0.1O1.95 composite cathode for intermediate-temperature solid oxide fuel cells

Fe- and Cu-doped SmBaCo₂O_5+δ (FC-SBCO)-Ce_0.9Gd_0.1O_1.95 (CGO) composites with various CGO contents (0-40 wt.%) are investigated as new cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) based on a Ce_0.9Gd_0.1O_1.95 electrolyte. The effect of CGO incorporation on the thermal expansion coefficient (TEC), electrochemical properties and thermal stability of the FC-SBCO-CGO composites is investigated. A composite cathode of 30 wt.% CGO-70 wt.% FC-SBCO (CS30-70) coated on a Ce_0.9Gd_0.1O_1.95 electrolyte shows the lowest area specific resistance (ASR), i.e., 0.049 Ω cm² at 700 °C. The TEC of the CS30-70 cathode is 14.1 × 10⁻⁶ °C⁻¹ up to 900 °C, which is a lower value than that of the FC-SBCO (16.6 × 10⁻⁶ °C⁻¹) counterpart. Long-term thermal stability and thermal cycle tests of the CS30-70 cathode are performed. Stable ARS values are observed during both type of test. An electrolyte-supported (300-μm thick) single-cell configuration of CS30-70/CGO/Ni-CGO delivers a maximum power density of 535 mW cm⁻² at 700 °C. The unique composite composition of CS30-70 demonstrates improved electrochemical performance and good thermal stability for IT-SOFCs.     

A potential interconnect material for solid oxide fuel cells: Nd0.75Ca0.25Cr0.98O3−δ

Chromium-deficient Nd_0.75Ca_0.25Cr_1−xO_3−δ (0.02 ≤ x ≤ 0.06) oxides are synthesized and assessed as a novel ceramic interconnect for solid oxide fuel cells (SOFCs). At room temperature, all the samples present single perovskite phase after sintering at 1600 °C for 10 h in air. Cr-deficiency significantly improves the electrical conductivity of Nd_0.75Ca_0.25Cr_1−xO_3−δ oxides. No structural transformation occurs in the Nd_0.75Ca_0.25Cr_1−xO_3−δ oxides in the temperature range studied. Among all the samples, the Nd_0.75Ca_0.25Cr_0.98O_3−δ sample with a relative density of 96.3% exhibits the best electrical conductivity of 39.0 and 1.6 S cm⁻¹ at 850 °C in air and hydrogen, respectively. The thermal expansion coefficient of Nd_0.75Ca_0.25Cr_0.98O_3−δ sample is 9.29 × 10⁻⁶ K⁻¹ in the temperature range from 30 to 1000 °C in air, which is close to that of 8 mol% yttria stabilized zirconia electrolyte (10.3 × 10⁻⁶ K⁻¹) and other cell components. The results indicate that Nd_0.75Ca_0.25Cr_0.98O_3−δ is a potential interconnect material for SOFCs.     

Contact resistivities of sputtered TiN and Ti---TiN metallizations on solar-cell-type-silicon

Contact resistivities of TiN and Ti---TiN contacts on a shallow junction solar-cell-type silicon substrate have been investigated. The contact materials were sputter-deposited. The method of the transmission line model was applied for contact resistivity measurements. The contact resistivity of the n⁺Si---TiN contact system was 2 × 10⁻³ Ωcm² ± 50 per cent and remained constant after annealing up to 700°C for 30 min. For the n⁺Si---Ti---TiN system, the contact resistivity of 9 × 10⁻⁴ Ωcm² ± 50 per cent was measured. A heat treatment of 700°C. 30 min decreases this value by one order of magnitude and the interposed Ti fully reacts with Si and forms a TiSi₂ layer. The voltage drop caused by the n⁺Si---TiN contact system in a standard non-concentrator solar cell is negligible. The n⁺Si---TiSi₂---TiN contact system should be acceptable for Si solar cells used at up to 100 times solar concentration.     

Thermoelectric properties of porous SiC/C composites

We developed a porous SiC/C composite by oxidizing a SiC/C composite made from a mixed powder of wood charcoal and SiO₂ (32–45 μm) by pulse current sintering at 1600 and 1800 °C under a N₂ atmosphere. The microstructures of the porous SiC/C composites with oxidation and the SiC/C composites without oxidation were analyzed by Raman spectroscopy and scanning electron microscopy (SEM). Raman spectra revealed the disappearance of excess carbon and the presence of β-SiC. The porous microstructure was monitored by SEM observation as a function of the heat treatment temperature. The thermoelectric properties of porous SiC/C composites with oxidation and SiC/C composites without oxidation were investigated by measuring the Seebeck coefficient, the electrical conductivity and thermal conductivity. The Seebeck coefficient of all samples revealed n-type conduction, and the absolute value of the Seebeck coefficient for the porous SiC/C samples with oxidation was much larger than that for the SiC/C samples without oxidation. For the electrical conductivity the reverse is true. Only the thermal conductivity of the SiC/C sample heated to 1800 °C without oxidation was high initially and stayed rather high. In general, the thermoelectric properties improved at higher measurement temperatures indicating their suitability for high-temperature thermoelectric conversion. A maximum figure of merit of 2.01×10⁻⁵ K⁻¹ was obtained at 700 °C in porous SiC/C samples sintered at 1800 °C with oxidation.     

Novel cobalt-free cathode materials BaCexFe1−xO3−δ for proton-conducting solid oxide fuel cells

A series of cobalt-free and low cost BaCe_xFe_1−xO_3−δ (x = 0.15, 0.50, 0.85) materials are successful synthesized and used as the cathode materials for proton-conducting solid oxide fuel cells (SOFCs). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BaCe_xFe_1−xO_3−δ cathode layer, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and the static air as the oxidant. Within all the cathode materials above, the cathode BaCe_0.5Fe_0.5O_3−δ shows the highest cell performance which could obtain an open-circuit potential of 0.99 V and a maximum power density of 395 mW cm⁻² at 700 °C. The results indicate that the Fe-doped barium cerates can be promising cathodes for proton-conducting SOFCs.     

Bulk p-CuInSe2 photo-electrochemical solar cells

Dense CuInSe₂ of high quality, prepared by the fusion technique in evacuated quartz ampoule from stoichiometric melt, crystallizes in the chalcopyrite structure. Compositional analysis carried out by secondary ion mass spectrometry (SIMS) and energy dispersive spectroscopy (EDS) indicates a uniform distribution of elements through the depth and a composition close to the stoichiometry. The diffuse reflectance spectrum gives a band gap at 0.94 eV. The electrical conductivity follows an Arrhenius-type law with activation energy of 23 meV in conformity with polarons hopping. Above 320 °C, CuInSe₂ undergoes an irreversible oxidation. The thermal variation of the thermopower indicates p-type behavior attributed to copper deficiency and a hole mobility μ_300 K of 0.133 cm² V⁻¹ s⁻¹, thermally activated. In KCl media, the compound exhibits an excellent chemical stability with a corrosion rate of 8 μmol cm⁻² month⁻¹. The photo-electrochemical properties, investigated for the first time on the ingots, confirm the p-type conductivity. From the capacitance measurements, the flat band potential (V_fb=−0.62V_SCE) and the holes density (N_A=4×10¹⁷ cm⁻³) were determined. The valence band, located at 4.43 eV below vacuum, is made up of mainly Se orbital with little admixture of Cu character. The change of the electrolyte causes a variation in the potential V_fb (dV_fb/dpH=−0.058 V pH⁻¹) indicating strong OH⁻ adsorption. The fill factor in S²⁻ media was found to be 0.54; such result was corroborated by semi-logarithmic plots.     

Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.     

Water incorporation and proton conductivity in titanium substituted barium indate

Water uptake in the perovskite-like oxygen deficient compounds Ba₂(In_1−xTi_x)₂O_5+x□_1−x (0 ≤ x < 0.7) (called BITx) was investigated by thermal gravimetric analysis (TGA) at equilibrium conditions and thermodynamic data of the hydration process were extracted. The change of the lattice volume upon hydration, inferred from X-ray diffraction data, appears as an important parameter for the characterization of perovskite-type proton conductors. The proton conductivity, the transport number and the proton diffusion coefficients for BITx compounds were determined from conductivity measurements performed under wet and dry atmosphere. The conductivity of Ba₂(In_1−xTi_x)₂O_5+x□_1−x compounds is mainly protonic up to 450 °C and the best level of proton conductivity was obtained for BIT02 with a value of 1.1 × 10⁻³ S cm⁻¹ at 450 °C.     

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3−δ electrolyte-based protonic ceramic membrane fuel cells with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

A stable, easily sintered perovskite oxide BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm⁻², and a low polarization resistance of the electrodes of 0.17 Ω cm² were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.     

La0.84Sr0.16MnO3−δ cathodes impregnated with Bi1.4Er0.6O3 for intermediate-temperature solid oxide fuel cells

La_0.84Sr_0.16MnO_3−δ–Bi_1.4Er_0.6O₃ (LSM–ESB) composite cathodes are fabricated by impregnating LSM electronic conducting matrix with the ion-conducting ESB for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The performance of LSM–ESB cathodes is investigated at temperatures below 750 °C by AC impedance spectroscopy. The ion-impregnation of ESB significantly enhances the electrocatalytic activity of the LSM electrodes for the oxygen reduction reactions, and the ion-impregnated LSM–ESB composite cathodes show excellent performance. At 750 °C, the value of the cathode polarization resistance (R_p) is only 0.11 Ω cm² for an ion-impregnated LSM–ESB cathode, which also shows high stability during a period of 200 h. For the performance testing of single cells, the maximum power density is 0.74 W cm⁻² at 700 °C for a cell with the LSM–ESB cathode. The results demonstrate the ion-impregnated LSM–ESB is one of the promising cathode materials for intermediate-temperature solid oxide fuel cells.     

Thermal cycle stability of BaO–B2O3–SiO2 sealing glass

Thermal cycle stability is very important for glass seals in planar solid oxide fuel cell (pSOFC) applications. In the present study, thermal cycle stability of a thermally stable sealing glass is investigated using a sealing fixture from 150 °C to 700 °C. SS410 alloy with the TEC (thermal expansion coefficient) of 12.2 × 10⁻⁶ K⁻¹ (room temperature to 700 °C) is used to evaluate the effect of TEC mismatch on the thermal cycle stability. The leak rates increase with thermal cycles and appear to be two different stages. Microstructure examinations are performed to investigate the degradation mechanism of the thermal cycle stability. It is found that the sealing glass interacts chemically with the SS410 alloy and the formation of BaCrO₄ new phase results in the rapid increase of the leak rates.