Structural, thermal and electrochemical properties of layered perovskite SmBaCo2O5+d, a potential cathode material for intermediate-temperature solid oxide fuel cells

The synthesis, conductivity properties, area specific resistance (ASR) and thermal expansion behaviour of the layered perovskite SmBaCo₂O_5+d (SBCO) are investigated for use as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The SBCO is prepared and shows the expected orthorhombic pattern. The electrical conductivity of SBCO exhibits a metal–insulator transition at about 200 °C. The maximum conductivity is 570 S cm⁻¹ at 200 °C and its value is higher than 170 S cm⁻¹ over the whole temperature range investigated. Under variable oxygen partial pressure SBCO is found to be a p-type conductor. The ASR of a composite cathode (50 wt% SBCO and 50 wt% Ce_0.9Gd_0.1O_2−d, SBCO:50) on a Ce_0.9Gd_0.1O_2−d (CGO91) electrolyte is 0.05 Ω cm² at 700 °C. An abrupt increase in thermal expansion is observed in the vicinity of 320 °C and is ascribed to the generation of oxygen vacancies. The coefficients of thermal expansion (CTE) of SBCO is 19.7 and 20.0 × 10⁻⁶ K⁻¹ at 600 and 700 °C, respectively. By contrast, CTE values for SBCO:50 are 12.3, 12.5 and 12.7 × 10⁻⁶ K⁻¹ at 500, 600 and 700 °C, that is, very similar to the value of the CGO91 electrolyte.     

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%.     

A glass frit-sealed dye solar cell module with integrated series connections

As the dye solar cell (DSC) technology progresses from laboratory-scale to large-area applications, long-term stability is one major obstacle. Especially for large-area DSC modules, stability is often a matter of hermetic sealing both between cells and for the whole module. Here we suggest glass frit as sealing material. Glass frit is thermally, mechanically and chemically very stable and can be applied via screen printing.DSC modules of 30×30 cm² with a glass frit as primary sealing material have been produced.It was shown that glass frit is applicable for the upscaling of the DSC technology to large areas. The thermal stability of the glass frit sealing and the integrated series connections was verified in a thermal cycling from −40 to 80 °C.The colouration process has been scaled up to 30×30 cm² by pumping the dye solution through the module using only two filling holes. By heating the module to 70 °C the filling of the module with electrolytes based on high viscous ionic liquids was demonstrated.     

New hybrid inorganic–organic polymer electrolytes based on Zr(O(CH2)3CH3)4, glycerol and EMIm-TFSI ionic liquid

This report presents detailed studies on the elemental analysis, vibrational spectroscopy, thermal stability and electrical spectroscopy of two new hybrid inorganic–organic polymers which have been synthesised by a sol–gel method using glycerol and zirconium(IV)butoxide as precursors. These materials have been doped by means of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIm-TFSI) ionic liquid (IL), which is insoluble in water. The elemental composition of the obtained polymers [Zr(C₆O₅H₁₁)] (1) and [Zr(C₁₁O₄H₃₁)] (2) has been determined by CHN analysis and by ICP-AES measurements. FT-IR and FT-Raman spectroscopy investigations have been performed to study the molecular structure of the polymers and the interactions of EMIm-TFSI with the host networks. Differential scanning calorimetry measurements show the presence of at least one glass transition temperature (T_g) in both 1 and 2 materials. The broadband dielectric spectroscopic measurements have been carried out between 10⁻² Hz to 10 MHz from −100 °C to 100 °C with a 5 °C step. The conductivities of the polymers 1 and 2 have been found to be in the order of 10⁻⁸ to 10⁻¹¹ S cm⁻¹ at 25 °C, so they can be defined as dielectric materials. After doping 2 with EMIm-TFSI, the conductivity at 25 °C of the obtained complex [Zr(C₁₁O₄H₃₁)]₁₅/(EMIm-TFSI) (2′) increased three orders of magnitude resulting ca. 10⁻⁵ S cm⁻¹. The permittivity spectra revealed two relaxation bands which were attributed to the α relaxation modes of the polymer networks.     

SiO2–Al2O3–Y2O3–ZnO glass sealants for intermediate temperature solid oxide fuel cell applications

In this study, eleven alkaline earth metal and B₂O₃-free SiO₂–Al₂O₃–Y₂O₃–ZnO glass sealants were prepared. The thermal stability, adhesion, and sealing properties of the glass systems with respect to SUS430 stainless steel (SUS430) were assessed for use in intermediate temperature solid oxide fuel cells (ITSOFCs). The glass transition points fell in the range of 694 °C and 833 °C, while the glass softening points, varying from 725 °C to 885 °C, decreased linearly with the ZnO/SiO₂ ratio. Among the glasses evaluated, the YAS1-50, YAS4-50, YAS5-50, and YAS5-90 glasses coupled with SUS430 showed fine adhesion and no detectable inter-diffusion across the interface. The coefficient of thermal expansion (CTE) of the YAS5-50 glass escalated from 7.01 to 9.30 × 10⁻⁶/K with 50 wt% Bi_1.5Y_0.5O₃ (BYO) fillers. The leak rates of the composite seals comprising the YAS5-50 glass and 50 wt% BYO fillers were measured at 700 °C after joining at 850 °C. The measurement used helium with a pressure at 1 psi across the glass seals and a slight load of 1.0 psi to minimize compressive seal effect on the glass. It appeared that a low leak rate of 0.052 sccm/cm was obtained and stayed unchanged as the system was soaked at 700 °C for 500 h, indicating a fine thermal stability against the extended duration benefited from the limited crystallization of the YAS5-50 glass. This promising long-term stability qualified the glass for use as SOFC seal.     

Electrochromic properties of heat-treated thin films of CeO2–TiO2–ZrO2 prepared by sol–gel route

CeO₂–TiO₂–ZrO₂ thin films were prepared using the sol–gel process and deposited on glass and ITO-coated glass substrates via dip-coating technique. The samples were heat treated between 100 and 500 °C. The heat treatment effects on the electrochromic performances of the films were determined by means of cyclic voltammetry measurements. The structural behavior of the film was characterized by atomic force microscopy and X-ray diffraction. Refractive index, extinction coefficient, and thickness of the films were determined in the 350–1000 nm wavelength, using nkd spectrophotometry analysis.Heat treatment temperature affects the electrochromic, optical, and structural properties of the film. The charge density of the samples increased from 8.8 to 14.8 mC/cm², with increasing heat-treatment temperatures from 100 to 500 °C. It was determined that the highest ratio between anodic and cathodic charge takes place with increase of temperature up to 500 °C.     

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.     

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.     

High performance layered SmBa0.5Sr0.5Co2O5+δ cathode for intermediate-temperature solid oxide fuel cells

The layered SmBa_0.5Sr_0.5Co₂O_5+δ (SBSC) perovskite oxide is synthesized by the Pechini method and investigated as a novel cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). A laboratory-sized Sm_0.2Ce_0.8O_1.9 (SDC)-based tri-layer cell of NiO–SDC/SDC/SBSC is operated from 500 to 700 °C fed with humidified H₂ (3% H₂O) as a fuel and the static ambient air as oxidant. A maximum power density of 1147 mW cm⁻² is achieved at 700 °C. The interfacial polarization resistance is as low as 1.01, 0.38, 0.16, 0.06 and 0.03 Ω cm² at 500, 550, 600, 650 and 700 °C, respectively. The experimental results indicate that SBSC is a very promising cathode material for IT-SOFCs.     

Heat treatment effects on the optical properties of Sol–gel Ta2O5 thin films

In this work optical properties of Ta₂O₅ thin films with respect to heat treatment temperature were investigated. Ta₂O₅ thin films were prepared by sol–gel process using dip-coated method with a constant speed of 107 mm/min. Optical properties have been calculated from optical transmission measurements as a function of heat treatment temperature. The refractive indices and absorption coefficients were affected by heat treatment. The refractive index at λ=550 nm increased from 1.84 to 2.04 and absorption coefficient increased from 241 to 5668 cm⁻¹ when heat treatment temperature increased from 100°C to 500°C. The thickness of the film decreased from 272 to 190 nm and their optical band gap decreased from 3.68±0.09 eV to 3.51±0.08 eV for the film heated from 100°C to 500°C.     

Layered GdBa0.5Sr0.5Co2O5+δ as a cathode for intermediate-temperature solid oxide fuel cells

The layered GdBa_0.5Sr_0.5Co₂O_5+δ (GBSC) perovskite oxides are synthesized by Pechini method and investigated as a novel cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The single cell of NiO–SDC (Sm_0.2Ce_0.8O_1.9)/SDC (20 μm)/GBSC (10 μm) is operated from 550 to 700 °C fed with humidified H₂ as fuel and the static air as oxidant. An open circuit voltage of 0.8 V and a maximum power density of 725 mW cm⁻² are achieved at 700 °C. The interfacial polarization resistance is as low as 0.88, 0.29, 0.13 and 0.05 Ω cm² at 550, 600, 650 and 700 °C, respectively. The ratio of polarization resistance to total cell resistance decreases with the increase in the operating temperature, from 60% at 550 °C to 21% at 700 °C, respectively. The experimental results indicate that GBSC is a promising cathode material for IT-SOFCs.     

B2O3-free SiO2–Al2O3–SrO–La2O3–ZnO–TiO2 glass sealants for intermediate temperature solid oxide fuel cell applications

In this study, the chemical and thermal stabilities of eleven B₂O₃-free SiO₂–Al₂O₃–SrO–La₂O₃–ZnO–TiO₂ glasses were investigated, and the adhesion and sealing properties of the glasses with respect to Gd_0.2Ce_0.8O_2−δ (GDC) electrolyte and SUS 430 stainless steel (SUS430) were evaluated for use in intermediate temperature solid oxide fuel cells (ITSOFCs). It was found that the major crystallites formed in the glasses were initiated during the joining process at 950 °C, and only slight changes were observed in the intensity of crystallite peaks for the glasses subsequently soaked at 700 °C for 200 h. Experiments on the glass sandwiched with GDC electrolyte and SUS430 indicated that the SALSTi11 and SALSZT10 glasses provided good adhesion along the interfaces after heat treatment. According to the results of leakage test, the seals with the SALSTi11 and SALSZT10 glasses at 700 °C for a duration of 500 h showed good thermal stability with low leak rates of 0.007 and 0.003 sccm/cm at 0.5 psi, respectively. This property indicates a highly promising long-term thermal stability qualifying the sealing materials for ITSOFC applications.     

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.     

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.     

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.     

Optical and electrochemical properties of V2O5:Ta Sol–Gel thin films

Vanadium and tantalum-doped vanadium pentoxide, V₂O₅ and V₂O₅:Ta thin films (2.5 and 5 mol% of Ta) were prepared using sol–gel dip-coating technique.The coating solutions were prepared by reacting vanadium (V) oxytripropoxide and tantalum ethoxide (V) as precursors using anhydrous isopropyl alcohol as solvent.The films were deposited on a transparent glass substrate with ITO conducting film by dip-coating technique, with a withdrawal of 20 cm/min from the vanadium–tantalum solution and heat treated at 300 °C for 1 h. The resulting films were characterized by cyclic voltammetry, optical spectroscopy and by X-ray diffraction analysis (XRD). XRD data show that the films thermally treated at 300 °C were crystalline.A charge density of 70 mC/cm² was obtained for the film with 5 mol% of Ta, with an excellent stability up to 1500 cycles.     

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.     

New proton conducting polymer blends and their fuel cell performance

Novel polymer blends based on aromatic polyethers with pyridine units have been prepared for their use as electrolytes after being doped with phosphoric acid for high temperature PEM fuel cells. They exhibit very good film-forming properties, mechanical integrity, high modulus up to 230 °C, high glass transition temperatures (up to 260 °C) and high thermal stability up to 400 °C. In addition to the above required properties, these novel materials show high oxidative stability and acid doping ability, enabling proton conductivity in the range of 10⁻² S cm⁻¹ at 130 °C. The preparation and fuel cell testing of membrane electrode assemblies, demonstrated very promising performance, and an initial study has shown the positive effect of humidity on the measured conductivity.     

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.     

Highly transparent and conductive Zn0.85Mg0.15O:Al thin films prepared by pulsed laser deposition

Zn_1−xMg_xO:Al thin films have been prepared on glass substrates by pulsed laser deposition (PLD). The effect of substrate temperature has been investigated from room temperature to 500 °C by analyzing the structural, optical and electrical properties. The best sample deposited at 250 °C shows the lowest room-temperature resistivity of 5.16×10⁻⁴ Ω cm, and optical transmittance higher than 80% in the visible region. It is observed that the optical band gap decreases from 3.92 to 3.68 eV when the substrate temperature increases from 100 to 500 °C. The probable mechanism is discussed.