Preparation and characterization of neodymium-doped ceria electrolyte materials for solid oxide fuel cells

The microstructure, thermal expansion, microhardness, indentation fracture toughness, and ionic conductivity of neodymium-doped ceria (NDC) prepared by coprecipitation were investigated. The results revealed that the average particle size (D_BET) ranged from 20.1 to 25.8 nm, crystallite dimension (D_XRD) varied from 17.5 to 20.7 nm, and the specific surface area distribution was from 31.25 to 40.27 m²/g for neodymium-doped ceria stacking powders. Dependence of lattice parameter, a, versus dopant concentration, x, of Nd³⁺ ion shows that these solid solutions obey Vegard's rule as a(x) = 5.4069 + 0.1642x for Ce_1?xNd_xO_2?(1/2)x for x = 0.05–0.25. For neodymium-doped ceria ceramics sintered at 1500 °C for 5 h, the bulk density was over 95% of the theoretical density. The maximum ionic conductivity, σ_800°C = 4.615 × 10^?2 S/cm, with the minimum activation energy, E_a = 0.794 eV was found for the Ce_0.75Nd_0.25O_1.875 ceramic. Trivalent, neodymium-doped ceria ceramics revealed high fracture toughness, the fracture toughness distribution was in the range of 6.236 ± 0.021 to 6.846 ± 0.017 MPa m^1/2. The high indentation fracture toughness of neodymium-doped ceria was attributed to crack deflection. Moreover, the porosity may influence the mechanical properties such as microhardness and fracture toughness. It was observed that as the porosity reduced, the microhardness and fracture toughness increased.     

Creep behaviour of membrane and substrate materials for oxygen separation units

Advanced oxygen separation units are based on thin mixed ionic–electronic conducting ceramic layers that are mechanically supported by a porous substrate. One of the most important aspects for the long-term stability at elevated temperatures is the creep behaviour, which was assessed in the current study for various potential membrane and substrate materials. Systematic creep tests were carried out in air in the temperature range 700–1200 °C, under compressive loads of 20–120 MPa. The steady-state strain rates were described by a standard creep equation. LSCF38, MgO and all investigated cerium oxides (CeO_2?δ and its three Gd-/Pr-doped variations: Ce_0.8Gd_0.2?xPr_xO_{2?0.5(0.2?x)?δ}, with x = 0, 0.1 and 0.2) satisfied at around 800 °C a creep limit criterion, suggested to be necessary to warrant reliable long-term stability for membrane systems, but only ceria materials and MgO fulfilled this requirement also at higher temperatures.     

Nitrate–citrate combustion synthesis of Ce1−xGdxO2−x/2 powder and its characterization

The structure, thermal expansion coefficients, and electric conductivity of Ce_1−xGd_xO_2−x/2 (x = 0–0.6) solid solution, prepared by the gel-combustion method, were investigated. The uniform small particle size of the gel-combustion prepared materials allows sintering into highly dense ceramic pellets at 1300 °C, a significantly lower temperature compared to that of 1600–1650 °C required for ceria solid electrolytes prepared by traditional solid state techniques. XRD showed that single-phase solid solutions formed in all the investigated range. The maximum conductivity, σ_600 °C = 5.26 × 10⁻³ S/cm, was found at x = 0.2. The thermal expansion coefficient, determined from high-temperature X-ray data, was 8.125 × 10⁻⁶ K⁻¹ at x = 0.2.     

Synthesis and electrical properties of Ce1−xGdxO2−x/2 (x = 0.05–0.3) solid solutions prepared by a citrate–nitrate combustion method

Ce_1?xGd_xO_2?x/2 (GDC) powders with different Gd³⁺ contents (x = 0.05–0.3) were prepared by a simple citrate–nitrate combustion method. The influence of the Gd³⁺ doping content on the crystal structure and the electrical properties of GDC were examined. Many analysis techniques such as thermal analysis, X-ray diffraction, nitrogen adsorption analysis, scanning electron microscopy and AC impedance analysis were employed to characterize the GDC powders. The crystallization of the GDC solid solution occurred below 350 °C. The GDC powders calcined at 800 °C showed a typical cubic fluorite structure. The lattice parameter of GDC exhibited a linear relationship with the Gd³⁺ content. As compared with that sintered at other temperatures, the GDC pellet that sintered at 1300 °C had a high relative density of 97%, and showed finer microstructure. The conductivity of GDC was firstly increased and then decreased with the increase of the Gd³⁺ content. The sintered GDC sample with the Gd³⁺ content of 0.25 exhibited the highest conductivity of 1.27 × 10^?2 S cm^?1 at 600 °C.     

Electronic conductivity,oxygen permeability and thermal expansion of Sr0.7Ce0.3Mn1−xAlxO3−δ

The maximum solubility of aluminum cations in the perovskite lattice of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ is approximately 15%. The incorporation of Al³⁺ increases oxygen ionic transport due to increasing oxygen nonstoichiometry, and decreases the tetragonal unit cell volume and thermal expansion at temperatures above 600 °C. The total conductivity of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2), predominantly electronic, decreases with aluminum additions and has an activation energy of 10.2–10.9 kJ/mol at 350–850 °C. Analysis of the electronic conduction and Seebeck coefficient of Sr_0.7Ce_0.3Mn_0.9Al_0.1O_3−δ, measured in the oxygen partial pressure range from 10⁻¹⁸ to 0.5 atm at 700–950 °C, revealed trends characteristic of broad-band semiconductors, such as temperature-independent mobility. The temperature dependence of the charge carrier concentration is weak, but exhibits a tendency to thermal excitation, whilst oxygen losses from the lattice have an opposite effect. The role of the latter factor becomes significant at temperatures above 800 °C and on reducing p(O₂) below 10⁻⁴ to 10⁻² atm. The oxygen permeability of dense Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ (x = 0–0.2) membranes, limited by both bulk ionic conduction and surface exchange, is substantially higher than that of (La, Sr)MnO₃-based materials used for solid oxide fuel cell cathodes. The average thermal expansion coefficients of Sr_0.7Ce_0.3Mn_1−xAl_xO_3−δ ceramics in air are (10.8–11.8) × 10⁻⁶ K⁻¹.     

Electrochemical and thermal characterization of doped ceria electrolyte with lanthanum and zirconium

Nanocomposites electrolytes consisting of La³⁺ and Zr⁴⁺ doped with ceria labelled as La_0.2 Ce_0.8 O_2-δ (LDC), Zr_0.2Ce_0.8O_2-δ (ZDC) and Zr_0.2La_0.2Ce_0.6O_2-δ (ZLDC) have been synthesized via a co-precipitation route. DC conductivity was studied with a four-probe method in the range of temperature 450–650 °C and maximum conductivity was found to be 0.81 × 10^?2 S.cm^?1 (LDC) > 0.32 × 10^?2 S.cm^?1 (ZLDC) > 0.15 × 10^?2 S.cm^?1 (ZDC) at a temperature of 650 °C, respectively. Further, electric behavior of doped and co-doped ceria electrolytes was investigated by A.C electrochemical impedance spectroscopy (frequency range ~ 0.1 Hz?4 MHz). The phase/structural identification of the material prepared was studied using X-ray diffraction and found ceria to possess a cubic fluorite structure. Scanning electron microscopy (SEM) was carried out to study its morphology and particle size (~ 90–120 nm). Thermal behavior on its change in weight and length with the temperature were studied by thermogravimetric analysis (TGA) and dilatometry respectively. Furthermore, thermal expansion coefficients (TECs) of prepared electrolytes are calculated and found as follows: 13.4 × 10^?6 °C^?1, 13.6 × 10^?6 °C^?1and 15.3 × 10^?6 °C^?1 for LDC, ZDC and ZLDC, respectively, in the temperature range 150–1150 °C.     

Effects of mechanical milling on preparation and properties of CuAl1−xFexO2 thermoelectric ceramics

CuAl_1?xFe_xO₂ (x = 0, 0.1, and 0.2) thermoelectric ceramics produced by a reaction-sintering process were investigated. Pure CuAlO₂ and CuAl_0.9Fe_0.1O₂ were obtained. Minor CuAl₂O₄ phase formed in CuAl_0.8Fe_0.2O₂. Addition of 10 mol% Fe lowered the sintering temperature obviously and enhanced the grain growth. At x = 0.1, electrical conductivity = 3.143 Ω^?1 cm^?1, Seebeck coefficient = 418 μV K^?1, and power factor = 5.49 × 10^?5 W m^?1 K^?2 at 600 °C were obtained. The reaction-sintering process is simple and effective in preparing CuAlO₂ and CuAl_0.9Fe_0.1O₂ thermoelectric ceramics for applications at high temperatures.     

Crystal structure and microwave dielectric properties of Zn0.9Ti0.8−xSnxNb2.2O8 ceramics

The crystal structure and microwave dielectric properties of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.00, 0.05, 0.10, 0.15) ceramics sintered at temperatures ranging from 1100 °C to 1140 °C for 6 h were investigated. A single phase with ixiolite structure was obtained. With the increase of Sn content, the dielectric constant decreased attributed to the decrease of dielectric polarizability. The Qf value decreased with the decrease of packing fraction and grain size. The temperature coefficient of resonant frequency (τ_f) increased due to the increase of the bond valence of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ ceramics. The excellent microwave dielectric properties of ? = 35.05, Qf = 49,100 GHz, τ_f = ?27.6 × 10^?6/°C were obtained for Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.05) specimens sintered at 1120 °C for 6 h.     

Synthesis and optical properties of Ce0.95Pr0.05−xMxO2 (M = Mn,Si) as potential ecological red pigments for coloration of plastics

Ecological red pigments Ce_0.95Pr_0.05?xM_xO₂ (M = Mn, Si) have been synthesized by conventional solid-state route and characterized by X-ray diffractometer, scanning electron microscope and UV–vis spectroscopy. Mn⁴⁺/Si⁴⁺ was incorporated into the CeO₂–PrO₂ system to tune the color properties of the pigments by shifting the optical absorption edge. Si⁴⁺ substitution blue shifts the absorption edge of Pr-doped ceria and shows bright reddish brown color. Mn⁴⁺ substitution stabilizes the absorption edge and exhibits dark brown hue. The coloring mechanism is based on the shift of charge transfer band of CeO₂ to higher wavelength by co-substitution of Pr⁴⁺ and tetravalent metal ions in ceria. Si co-doped pigments possess smaller particles and hence exhibit more lightness compared to Mn co-doped samples. The reddish brown pigments exhibit very good coloring performance in polymer matrix. These Ce_0.95Pr_0.05?xM_xO₂ (M = Mn, Si) pigments have potential to be used as ecological red pigments for coloration of plastics.     

Mesoporous CexZr1−xO2 solid solutions supported CuO nanocatalysts for toluene total oxidation

Mesoporous Ce_xZr_1−xO₂ solid solutions were prepared by the surfactant-assisted method and used as support of CuO nanocatalysts for catalytic total oxidation of toluene. The prepared CuO/Ce_xZr_1−xO₂ catalysts have a wormhole-like mesoporous structure with high surface area and uniform pore size distribution, and the CuO nanoparticles were highly dispersed on the surface of Ce_xZr_1−xO₂. The doping of ZrO₂ in CeO₂ promotes the dispersion of active copper species and enhances the reducibility of copper species. The effect of Ce/Zr ratio, calcination temperature and CuO loading amount on the catalytic performance of CuO/Ce_xZr_1−xO₂ was investigated in detail. The 400 °C-calcined 8%CuO/Ce_0.8Zr_0.2O₂ catalyst exhibits the highest activity with the complete toluene conversion temperature of 275 °C at the condition of GHSH = 33,000 h⁻¹ and the toluene concentration of 4400 ppm. The interfacial interaction between CuO and the Ce_xZr_1−xO₂ support, highly dispersed CuO nanoparticles and the nature of the support contribute to the high catalytic activity of mesoporous CuO/Ce_xZr_1−xO₂ nanocatalysts.     

Electrochemical performance of intermediate temperature micro-tubular solid oxide fuel cells using porous ceria barrier layers

We describe the manufacture and electrochemical characterization of micro-tubular anode supported solid oxide fuel cells (mT-SOFC) operating at intermediate temperatures (IT) using porous gadolinium-doped ceria (GDC: Ce_0.9Gd_0.1O_2−δ) barrier layers. Rheological studies were performed to determine the deposition conditions by dip coating of the GDC and cathode layers. Two cell configurations (anode/electrolyte/barrier layer/cathode): single-layer cathode (Ni–YSZ/YSZ/GDC/LSCF) and double-layer cathode (Ni–YSZ/YSZ/GDC/LSCF–GDC/LSCF) were fabricated (YSZ: Zr_0.92Y_0.16O_2.08; LSCF: La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ). Effect of sintering conditions and microstructure features for the GDC layer and cathode layer in cell performance was studied. Current density–voltage (j–V) curves and impedance spectroscopy measurements were performed between 650–800 °C, using wet H₂ as fuel and air as oxidant. The double-cathode cells using a GDC layer sintered at 1400 °C with porosity about 50% and pores and grain sizes about 1 μm, showed the best electrochemical response, achieving maximum power densities of up to 160 mW cm⁻² at 650 °C and about 700 mW cm⁻² at 800 °C. In this case GDC electrical bridges between cathode and electrolyte are preserved free of insulating phases. A preliminary test under operation at 800 °C shows no degradation at least during the first 100 h. These results demonstrated that these cells could compete with standard IT-SOFC, and the presented fabrication method is applicable for industrial-scale.     

Electrochemical and microstructural characteristics of nanoperovskite oxides Ba0.2Sr0.8Co0.8Fe0.2O3−δ (BSCF) for solid oxide fuel cells

Nanoperovskite oxides, Ba_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (BSCF), were synthesized via the co-precipitation method using Ba, Sr, Co, and Fe nitrates as precursors. Next, half cells were fabricated by painting BSCF thin film on Sm_0.2Ce_0.8O_x (samarium doped ceria, SDC) electrolyte pellets. X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical impedance spectroscopy (EIS) measurements were carried out on the BSCF powders and pellets obtained after sintering at 900 °C. Investigations revealed that single-phase perovskites with cubic structure was obtained in this study. The impedance spectra for BSCF/SDC/BSCF cells were measured to obtain the interfacial area specific resistances (ASR) at several operating temperatures. The lowest values of ASR were found to be 0.19 Ω cm², 0.14 Ω cm² 0.10 cm², 0.09 Ω cm² and 0.07 Ω cm² at operating temperatures of 600 °C, 650 °C, 700 °C, 750 °C and 800 °C, respectively. The highest conductivity was found for cells sintered at 900 °C with an electrical conductivity of 153 S cm^?1 in air at operating temperature of 700 °C.     

Synthesis and electrical properties of co-doping with La3+, Nd3+, Y3+, and Eu3+ citric acid-nitrate prepared samarium-doped ceria ceramics

Fluorite oxides Ce_0.8Sm_0.1Ln_0.1O_1.9 (denoted as SDC for singular doping and LnSDC for Ln=La, Nd, Y and Eu), were prepared by the citric acid–nitrate combustion reaction to act as electrolytes for intermediate-temperature solid oxide fuel cells (IT-SOFC). The thermal decomposition, phase identification, morphology, density, particle size distribution and electrical properties of the samples were studied by TGA/TDA, XRD, SEM, the Archimedes method, a laser size analyzer and Impedance spectroscopy, respectively. All crystallite powders that calcined at 800 °C had a cubic fluorite structure; the average crystallite size was between 63 and 68.5 nm. The pellets were then sintered at 1400 °C in air for 7 h. The relative densities of these pellets were over 95%, which was in good agreement with the results of the SEM. The impedance measurements were performed in an open circuit using two electrode configurations. The results showed that Ce_0.8Sm_0.1La_0.1O_1.9 had the highest electrical conductivity, σ_700 °C, equal to 6.59×10^?2 S cm^?1 and the lowest activation energy equal to 0.85 eV. It was therefore concluded that co-doping with the appropriate rare-earth cations can further improve the electrical properties of ceria electrolytes.     

Effect of preparation route on the microstructure and electrical conductivity of co-doped ceria

Dense Ce_0.8Sm_0.1Gd_0.1O_2?δ electrolytes were fabricated by sintering of CeO₂ solid solutions which were prepared from metal nitrates and NaOH using self propagating room temperature synthesis (SPRT). Three different routes were employed to obtain CeO₂ solid solution powders: (I) hand mixing of reactants, (II) ball milling of reactants and (III) ball milling of Ce_0.8Sm_0.2O_2?δ and Ce_0.8Gd_0.2O_2?δ solid solutions previously prepared by ball milling of corresponding nitrates and NaOH. Density measurements showed that ball milling, which is more convenient than hand mixing, is an effective way to obtain almost full dense samples after presureless sintering at 1550 °C for 1 h. These samples had larger grain size and consequently higher conductivity than the samples obtained by hand mixing. The highest conductivity of 2.704×10^?2 (Ω cm)^?1was measured at 700 °C in a sample prepared by route II. It was found that reduced grain size in samples obtained by hand mixing leads to a decrease in grain boundary conductivity and therefore decrease in the total conductivity. The results showed that mixing of single doped ceria solid solutions improved densification and inhibited grain growth.     

Electrolyte materials for solid oxide fuel cells derived from metal complexes: Gadolinia-doped ceria

Gadolinia doped ceria (GDC) powders with different gadolinium contents were successfully prepared by the thermal decomposition of ceria complexes. All the calcined powder samples were found to be ceria-based solid-solutions having a fluorite-type structure. The powders were cold-isostatically pressed and sintered in air at 1500 °C for 5 h to attain a sintered density of about 90% of its theoretical value. The electrical conductivity of the GDC pellets in air was studied as a function of temperature in the 225–700 °C range, by using two-probe electrochemical impedance spectroscopy measurements. The highest total conductivity (σ_600 °C = 0.025 S/cm) was found for the Ce_0.85Gd_0.15O_1.925 composition.     

Performance evaluation of Sm0.5Sr0.5CoO3−δ fibers with embedded Sm0.2Ce0.8O1.9 particles as a solid oxide fuel cell composite cathode

Sm_0.2Ce_0.8O_1.9 (SDC)–embedded Sm_0.5Sr_0.5CoO_3?δ (SSC) composite fibers were successfully fabricated by electrospinning using commercial SDC nanopowders and an SSC precursor gel containing polyvinyl alcohol (PVA) and hydrated metal nitrate. After calcination of the composite fibers at 800 °C, the fibers of 300 ± 80 nm in diameter with a well-developed SSC cubic-perovskite structure and fluorite SDC were successfully obtained. An anode-supported single cell composed of NiO–Gd_0.2Ce_0.8O_1.9 (GDC)/GDC/SSC–SDC fibers was fabricated, and its electrochemical performance was evaluated. The maximum power densities were 1250 and 360 mW/cm² at 700 and 550 °C, respectively, which we ascribe to the excellent properties of the SSC fibers with embedded SDC particles such as a highly porous and continuous structure promoting mass transport and a charge transfer reaction.     

Ce0.9Gd0.1O1.95 supported La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes for solid oxide fuel cells

Lanthanum-based iron- and cobalt-containing perovskite has a high potential as a cathode material because of its high electro-catalytic activity at a relatively low operating temperature in solid oxide fuel cells (SOFCs) (600–800). To enhance the electro-catalytic reduction of oxidants on La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF), Ga doped ceria (Ce_0.9Gd_0.1O_1.95, GDC) supported LSCF (15LSCF/GDC) is successfully fabricated using an impregnation method with a ratio of 15 wt% LSCF and 85 wt% GDC. The cathodic polarization resistances of 15LSCF/GDC are 0.015 Ω cm², 0.03 Ω cm², 0.11 Ω cm², and 0.37 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The simply mixed composite cathode with LSCF and GDC of the same compositions shows 0.05 Ω cm², 0.2 Ω cm², 0.56 Ω cm², and 1.20 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The fuel cell performance of the SOFC with 15LSCF/GDC shows maximum power densities of 1.45 W cm^?2, 1.2 W cm^?2, and 0.8 W cm^?2 at 780 °C, 730 °C, and 680 °C, respectively. GDC supported LSCF (15LSCF/GDC) shows a higher fuel cell performance with small compositions of LSCF due to the extension of triple phase boundaries and effective building of an electronic path.     

Microwave dielectric properties of novel temperature stable high Q Li2Mg1−xZnxTi3O8 and Li2A1−xCaxTi3O8 (A = Mg,Zn) ceramics

The Li₂Mg_1?xZn_xTi₃O₈ (x = 0–1) and Li₂A_1?xCa_xTi₃O₈ (A = Mg, Zn and x = 0–0.2) ceramics are synthesized by solid-state ceramic route and the microwave dielectric properties are investigated. The Li₂MgTi₃O₈ ceramic shows ?_r = 27.2, Q_u × f = 42,000 GHz, and τ_f = (+)3.2 ppm/°C and Li₂ZnTi₃O₈ has ?_r = 25.6, Q_u × f = 72,000 GHz, and τ_f = (?)11.2 ppm/°C respectively when sintered at 1075 °C/4 h. The Li₂Mg_0.9Zn_0.1Ti₃O₈ dielectric ceramic composition shows the best dielectric properties with ?_r = 27, Q_u × f = 62,000 GHz, and τ_f = (+)1.1 ppm/°C. The effect of Ca substitution on the structure, microstructure and microwave dielectric properties of Li₂A_1?xCa_xTi₃O₈ (A = Mg, Zn and x = 0–0.2) has also been investigated. The materials reported in this paper are excellent in terms of dielectric properties and cost of production compared to commercially available high Q dielectric resonators.     

Sol–gel synthesis and phase composition of ultrafine ceria-doped zirconia powders for functional ceramics

Ultrafine ceria-doped zirconia powders with the general formula Ce_xZr_1?xO₂ oriented for functional ceramic materials for different purposes were prepared by modified sol–gel synthesis with use of monoethanolamine or tetraethylammonium hydroxide. All powders were high crystallized single-phase systems with average crystallite size 8–11 nm. It was established that doping of zirconia by ceria led to a decrease in the crystallite size. At the same time the nature of the zirconium salt anion has little effect on crystallite size. However, only powders obtained from zirconyl chloride had crystallites with sizes below 10 nm. When x = 0.150–0.155, a sharp increase in the crystallite size was observed regardless of the used organic components. Use of tetraethylammonium hydroxide resulted in formation of Ce_xZr_1?xO₂ crystallites of 2–3 nm smaller than that which was obtained in the presence of monoethanolamine.