Study of Ln0.6Sr0.4Co0.8Mn0.2O3-δ (Ln=La, Gd, Sm or Nd) as the cathode materials for intermediate temperature SOFC

Perovskite type oxides Ln_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ (Ln=La, Gd, Sm, or Nd) have been prepared by the solid state reaction of corresponding oxides. The crystal parameters of the compositions were determined by XRD powder diffraction, which revealed that all the compositions have orthorhombic structure. The reaction test of all samples with Ce_0.8Gd_0.2O_1.9 was carried out at 1200 °C for 48 h, and no reaction product was detected by XRD. The change in mass of La_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ as a function of temperature was determined by thermogravimetric analysis (TGA). The electrical conductivity of the sintered samples were measured as a function of temperature from 200 to 1000 °C. The highest conductivity of about 1400 S cm⁻¹ was found in La_0.6Sr_0.4Co_0.8Mn_0.2O_3−δ. The cathodic polarization of these oxides electrodes deposited on Ce_0.8Gd_0.2O_1.9 tablet was studied at 500-800 °C in air.     

Electrical properties of thick-film NTC thermistor composed of Ni0.8Co0.2Mn2O4 ceramic: Effect of inorganic oxide binder

The thick-film NTC thermistors were prepared by screen printing Ni_0.8Co_0.2Mn₂O₄ ceramic on the alumina. The influence of inorganic oxide binder composition and thickness of thermistor layer on the thermistor constant and initial resistivity are studied. The relation between the resistivity (ρ) and the absolute temperature for the prepared thick-film thermistor comply with Arrhenius equation. The room temperature sheet resistivities of the thick films were in the range 0.56-7.45 MΩ cm and temperature sensitivity index in the range 1492-3335 K. Binder composition dependent agglomeration of microcrystallites is observed in the microstructure of the thick-film Ni_0.8Co_0.2Mn₂O₄ ceramic. The spinel ceramic was prepared by oxalate co-precipitation and sintering.     

Synthesis, structure, and electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2 prepared by thermal polymerization

A thermal polymerization route was adopted to synthesize layered LiNi_1/3Co_1/3Mn_1/3O₂ materials. After annealing the polymer gel containing metal salts at different temperatures from 850 to 1000 °C for different time between 6 and 25 h, powders of pure α-NaFeO₂ phase were obtained. The crystal structure, morphology and electrochemical properties of the products were investigated by XRD, SEM, electrochemical cell cycling and AC impedance spectroscopy. It is found that the powder annealed at 950 °C for 15 h shows the best electrochemical property with the first specific discharge capacity of 188 mAh/g at C/10 and 87% retention after 100 cycles. It exhibits good rate capability with the specific capacity of 169 mAh/g at 1 C and 110 mAh/g at 6 C. Adopting a slowly cooling procedure during the powder annealing can improve the electrochemical performance of the LiNi_1/3Co_1/3Mn_1/3O₂ powder.     

Electrochemical behaviors of Li[Li(1−x)/3Mn(2−x)/3Nix/3Cox/3]O2 cathode series (0 < x < 1) synthesized by sucrose combustion process for high capacity lithium ion batteries

A mixed cathode material between Li₂MnO₃ and Li[Mn_1/3Ni_1/3Co_1/3]O₂ for high capacity lithium secondary batteries was introduced in this study. It was prepared using the sucrose combustion process because this is a simple process. The oxidation states of Mn, Co and Ni ions in the pristine Li[Li_(1−x)/3Mn_(2−x)/3Ni_x/3Co_x/3]O₂ compounds were confirmed to be tetravalent, trivalent and divalent, respectively, via XANES measurements. Electrochemical charge/discharge studies showed that the highest first discharge capacity of 224 mAh/g was obtained in composition of x = 0.5 at a 0.2 C rate. The oxidation state of the Co and Ni ions in the Li[Li_1/6Mn_1/2Ni_1/6Co_1/6]O₂ changed to higher oxidation states, but that of the Mn ions did not change.     

Microwave-assisted synthesis of cobalt oxalate nanorods and their thermal conversion to Co3O4 rods

Cobalt oxalate nanorods have been successfully synthesized by a simple microwave-assisted solution approach using an ionic liquid 1-n-butyl-3-methyl imidazolium tetrafluoroborate. Upon thermal decomposition at 400 °C, cobalt oxalate nanorods could be converted to Co₃O₄ rods consisting of nanoparticles. The products were characterized using X-ray powder diffraction, transmission electron microscopy, thermogravimetric analysis and differential scanning calorimetric analysis.     

Effects of annealing temperature on microstructure and electrical properties of Mn-Co-Ni-O thin films

Mn_1.85Co_0.3Ni_0.85O₄ (MCN) thin films were prepared on Al₂O₃ substrates by chemical solution deposition method at different annealing temperature (650, 700, 750 and 800 °C). Effects of annealing temperature on microstructure and electrical properties of MCN thin films were investigated. The MCN thin film annealed at 750 °C is of good crystallization and compact surface. It shows lower resistance (4.8 MΩ) and higher sensitivity (3720.6 K) than those of other prepared films. It also has small aging coefficient (3.7%) after aging at 150 °C for 360 h. The advantages of good properties make MCN thin film very promising for integrated devices.     

Effects of Cr2O3 doping on the electrical properties and the temperature stabilities of PNW-PMN-PZT ceramics

The ceramics with 0.90Pb(Zr_0.50Ti_0.50)O₃-0.07Pb(Mn_1/3Nb_2/3)O₃-0.03Pb(Ni_1/2W_1/2)O₃ were prepared by adding Cr₂O₃. The effects of Cr₂O₃ doping on the phase structure, the microstructure and the electrical properties of ceramics were investigated. Meanwhile, the temperature stabilities of the resonant frequency (f_r) and the electromechanical coupling factor (K_p) were studied. The results showed that the better temperature stability could be obtained at x = 0.2 wt.% when the calcining temperature was 800 °C and the sintering temperature was 1150 °C. The parameters were Δf_r/f_r25 °C = −0.17% and ΔK_p/K_p25 °C = −1.39%. Moreover, the optimized electrical properties were also achieved, which were K_P = 0.54, Q_m = 1730, d₃₃ = 330 pC/N, ?_r = 2078 and tan δ = 0.0052. The optimized properties make the ceramics with this composition to be a good candidate for high power piezoelectric transformers applications.     

Microwave hydrothermal synthesis of nanoporous cobalt oxides and their gas sensing properties

In this paper, the precursors were synthesized by microwave hydrothermal method using Co(NO₃)₂·6H₂O as raw material, CO(NH₂)₂ and KOH as precipitants, respectively. The precursors and calcined products were characterized by XRD, FESEM, and BET-BJH. The results show that both constituent and synthetic condition can determine the products morphology. When using KOH as precipitant, hollow Co₃O₄ nanorings were obtained whose precursor was synthesized at 140 °C for 3 h and calcined at 500 °C in air for 2 h. While using CO(NH)₂, Co₃O₄ like-nanochains were obtained whose precursor was synthesized at 110 °C for 1 h and calcined at 420 °C in air for 2 h, and Co₃O₄ nanosheets were obtained while their precursor was synthesized at 140 °C for 3 h and calcined at 500 °C in air for 2 h. The sensitivity test of Co₃O₄ to alcohol reveals that the hollow Co₃O₄ nanorings show the best sensitivity, porous Co₃O₄ like-nanochains are superior to that of the porous nanosheets.     

Elaboration, by tape casting, and thermal characterization of a solid oxide fuel half-cell for low temperature applications

In the past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cell (SOFC) down to about 700 °C. In this respect, materials with a high ionic conduction at intermediate temperature have to be found and the processes to elaborate fuel cells, using these new materials, have to be developed.Apatite materials (La_10−xSr_x(SiO₄)₆O_2±δ) are attractive candidates for solid electrolyte working at intermediate temperature. The ceramic powder was produced by solid state reaction and was tape cast to obtain green sheets.Concerning the cathode, a perovskite oxide (La_1−xSr_xMn_1−yCo_yO_3−δ) has been chosen. The perovskite powder was also shaped by tape casting with the introduction of a pore forming agent (corn-starch) to obtain the required porosity in the sintered cathode.The co-firing of the electrolyte/cathode half-cell in air at 1400 °C-2 h gives a flat sample with a dense apatite (98.2%), a 42.7% porous cathode and neither delamination nor chemical reactivity between electrolyte and cathode materials.The dimensional behaviour of the electrolyte material is stable for an oxygen partial pressure ranging from 10⁻¹⁰ to 0.21 atmosphere, from room temperature to 700 °C. The thermal expansion coefficients of the electrolyte and cathode materials are rather close (Δα = 2.8 × 10⁻⁶ K⁻¹) under air.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Effect of B-site doping on Sm0.5Sr0.5MxCo1−xO3−δ properties for IT-SOFC cathode material (M = Fe, Mn)

The crystal structure, thermal expansion rate, electrical conductivity and electrochemical performance of Sm_0.5Sr_0.5M_xCo_1−xO_3−δ (M = Fe, Mn) have been investigated. Two crystal structures have been observed in the specimens of Sm_0.5Sr_0.5Fe_xCo_1−xO_3−δ (SSFC) at room temperature, the perovskite structure of SSFC has an orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9. The specimens of Sm_0.5Sr_0.5Mn_xCo_1−xO_3−δ (SSMC) crystallize in an orthorhombic structure. The adjustment of thermal expansion rate to electrolyte, which is one of the main problems of SSC, can be achieved to lower TEC values with more Fe and Mn substitution. Especially, Sm_0.5Sr_0.5Mn_0.8Co_0.2O_3−δ exhibits good thermal compatibility with La_0.8Sr_0.2Ga_0.8Mg_0.2O₃. High electrical conductivities are obtained for all the specimens and they demonstrate above 100 S/cm at 800 °C in SSFC system. The polarization resistance increases with increasing Mn content, Nevertheless, the polarization resistance of SSFC increases with increasing Fe content, but when the amount of Fe reaches to 0.4, the maximum is obtained while the resistance will decrease when the amount of Fe reaches above 0.4. Sm_0.5Sr_0.5Fe_0.8Co_0.2O_3−δ electrode exhibits high catalytic activity for oxygen reduction operating at temperature from 700 to 800 °C.     

High sensitivity chlorine gas sensors using CdIn2O4 thick film prepared by co-precipitation method

Gas-sensing properties to dilute Cl₂ have been investigated for CdIn₂O₄ thick film sensors prepared by co-precipitation method. Cadmium nitrate and indium nitrate were mixed in de-ionized water. The 0.1 M NaOH was added to the mixed solution. The co-precipitate obtained was washed, filtered, dried, and calcined at 600-900 °C for 4 h. The CdIn₂O₄ sensor prepared using the powder calcined at 600 °C showed high sensitivity (S=R_g/R_a) to dilute Cl₂ at 250 °C. In particular, the CdIn₂O₄ sensor showed the sensitivity as high as 1200 even to 0.2 ppm Cl₂. The crystal structure and surface morphology were examined by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Magnetic,oxidation and reduction behavior of spinel Ni–Cu manganite NixCu1-xMn2O4 powders

Nickel copper manganites, Ni_xCu_1-xMn₂O₄ (where 0 ≤ X ≤ 1), powders have been synthesized via co-precipitation method. The formed particles were obtained from the precipitate precursors annealed at 800 °C for 2 h. The prepared powders were tested for the catalytic oxidation of carbon monoxide (CO) into carbon dioxide (CO₂). The results indicated that the intermediate compositions displayed better catalytic activity than the end compositions for CO oxidation due to the phenomena of synergism. The composition of x = 0.3 and 0.5 showed rapid rise in CO conversion with temperature; about 40% conversion was achieved at 200 °C for the produced manganite sample of chemical composition Cu₀.₇Ni₀.₃Mn₂O₄. A correlation between magnetic properties and hydrogen reduction of manganites was demonstrated. Magnetic properties of reduced manganite were found to be duplicated. The saturation magnetization of reduced NiMn₂O₄ into Ni/MnO was duplicated of order 15 times from initial value.     

Surface and catalytic properties of MoO3/Al2O3 system doped with Co3O4

Thermal solid-solid interactions in cobalt treated MoO₃/Al₂O₃ system were investigated using X-ray powder diffraction. The solids were prepared by wet impregnation method using Al(OH)₃, ammonium molybdate and cobalt nitrate solutions, drying at 100 °C then calcination at 300, 500, 750 and 1000 °C. The amount of MoO₃, was fixed at 16.67 mol% and those of cobalt oxide were varied between 2.04 and 14.29 mol% Co₃O₄. Surface and catalytic properties of various solid samples precalcined at 300 and 500 °C were studied using nitrogen adsorption at −196 °C, conversion of isopropanol at 200-500 °C and decomposition of H₂O₂ at 30-50 °C.The results obtained revealed that pure mixed solids precalcined at 300 °C consisted of AlOOH and MoO₃ phases. Cobalt oxide-doped samples calcined at the same temperature consisted also of AlOOH, MoO₃ and CoMoO₄ compounds. The rise in calcination temperature to 500 °C resulted in complete conversion of AlOOH into very poorly crystalline γ-Al₂O₃. The further increase in precalcination temperature to 750 °C led to the formation of Al₂(MoO₄)₃, κ-Al₂O₃ besides CoMoO₄ and un-reacted portion of Co₃O₄ in the samples rich in cobalt oxide. Pure MoO₃/Al₂O₃ preheated at 1000 °C composed of MoO₃-αAl₂O₃ solid solution (acquired grey colour). The doped samples consisted of the same solid solution together with CoMoO₄ and CoAl₂O₄ compounds.The increase in calcination temperature of pure and variously doped solids from 300 to 500 °C increased their specific surface areas and total pore volume which suffered a drastic decrease upon heating at 750 °C. Doping the investigated system with small amounts of cobalt oxide (2.04 and 4 mol%) followed by heating at 300 and 500 °C increased its catalytic activity in H₂O₂ decomposition. This increase, measured at 300 °C, attained 25.4- and 12.9-fold for the solids precalcined at 300 and 500 °C, respectively. The increase in the amount of dopant added above this limit decreased the catalytic activity which remained bigger than those of un-treated catalysts. On the other hand, the doping process decreased the catalytic activity of treated solids in isopropanol conversion especially the catalysts precalcined at 300 °C. This treatment modified the selectivities of treated solids towards dehydration and dehydrogenation of reacted alcohol.The activation energies of H₂O₂ decomposition were determined for pure and variously doped solids. The results obtained were discussed in light of induced changes in chemical composition and surface properties of the investigated system due to doping with cobalt oxide.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Fine Fe16N2 powder prepared by low-temperature nitridation

α-Fe was prepared by reduction of a fine γ-Fe₂O₃ powder under hydrogen at 500 °C for 8 h. The α-Fe fine powder, about 100 nm in crystallite size, was then nitrided under an ammonia flow at 130 °C for 100 h. X-ray single-phase Fe₁₆N₂ was obtained with a magnetization value of 225 emu/g at room temperature under a magnetic field of 15 kOe. The Mössbauer spectrum at room temperature could be resolved into three sets of hyperfine fields with an average magnetic moment of 2.52 μ_B. An additional paramagnetic component was present in the spectrum with an area ratio of 19%.     

Dielectric properties of CaCu3Ti4−xCoxO12 (x = 0.10, 0.20, and 0.30) synthesized by semi-wet route

Undoped CaCu₃Ti₄O₁₂ and cobalt doped CaCu₃Ti_4−xCo_xO₁₂ (CCTCO) with x = 0.10, 0.20 and 0.30 were prepared by semi-wet route for the first time using solid TiO₂ powder and metal nitrate solutions. XRD analysis confirmed the formation of single-phase material in the samples sintered at 900 °C for 6 h. Structure does not change on doping with cobalt and it remains cubic in all the three compositions studied. Lattice parameter increases slightly with cobalt doping. SEM micrographs of the CaCu₃Ti_4−xCo_xO₁₂ samples show that the grain size is in the range of 2–8 μm for these samples. EDX studies show the percentage of elements along with the grain and grain boundary, which confirm the rich phase of copper oxide at grain boundaries. Dielectric properties have been measured as a function of temperature and frequency.     

Composition dependent phase connectivity, dielectric and magnetoelectric properties of magnetoelectric composites with Pb(Mg1/3Nb2/3)0.67Ti0.33O3 as piezoelectric phase

Ferrite (Ni_0.6Co_0.4Fe₂O₄) phase, ferroelectric (Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃) phase and magnetoelectric composites of (x)Ni_0.6Co_0.4Fe₂O₄ + (1 − x)Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ with x = 0.15, 0.30 and 0.45 were prepared using solid-state reaction technique. Presence of Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ was confirmed using X-ray diffraction technique. The scanning electron microscopic images were used to study the microstructure of the composites. Connectivity scheme present in the magnetoelectric (ME) composites are discussed from the microscopic images. Variation of dielectric constant and dielectric loss with temperature for all the composites was studied. Here we report the effect of Ni_0.6Co_0.4Fe₂O₄ mole fraction on connectivity schemes between Ni_0.6Co_0.4Fe₂O₄ and Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composite. The variation of magnetoelectric voltage coefficient with dc magnetic field shows peak behaviour. The maximum value of magnetoelectric voltage coefficient of 9.47 mV/cm Oe was obtained for 0.15Ni_0.6Co_0.4Fe₂O₄ + 0.85Pb(Mg_1/3Nb_2/3)_0.67Ti_0.33O₃ composites. Finally we have co-related the effect of Ni_0.6Co_0.4Fe₂O₄ content and dielectric properties on magnetoelectric voltage coefficient.     

Effect of the sintering temperature on the properties of Ce0.85La0.10Ca0.05O2−δ electrolyte material

Rare earth and alkaline earth co-doped Ce_0.85La_0.10Ca_0.05O_2−δ electrolyte material with the powder obtained by solid-state reaction method was sintered at 1300, 1400, 1500 and 1600 °C respectively. The results showed that the ionic conductivity of the sample sintered at 1400 °C was slightly lower compared to that sintered at 1500 °C in the temperature range of 300-550 °C, while the sample sintered at 1400 °C showed the highest ionic conductivity in all the samples above 550 °C. The ionic conductivity of ∼0.021 S/cm at 600 °C and the relative density of 98.2% were observed for the sample sintered at 1400 °C. In addition, the highest flexural strength with 145 MPa was also obtained for the sample sintered at 1400 °C. It suggested that the sintering temperature for Ce_0.85La_0.10Ca_0.05O_2−δ electrolyte may be reduced to as low as 1400 °C with desired properties.