Semiconductor Fe-doped SrTiO3-δ perovskite electrolyte for low-temperature solid oxide fuel cell (LT-SOFC) operating below 520 °C

High-temperature operation of solid oxide fuel cells causes several degradation and material issues. Lowering the operating temperature results in reduced fuel cell performance primarily due to the limited ionic conductivity of the electrolyte. Here we introduce the Fe-doped SrTiO_3-δ (SFT) pure perovskite material as an electrolyte, which shows good ionic conduction even at lower temperatures, but has low electronic conduction avoiding short-circuiting. Fuel cell fabricated using this electrolyte exhibits a maximum power density of 540 mW/cm² at 520 °C with Ni-NCAL electrodes. It was found that the Fe-doping into the SrTiO_3-δ facilitates the creation of oxygen vacancies enhancing ionic conductivity and transport of oxygen ions. Such high performance can be attributed to band-bending at the interface of electrolyte/electrode, which suppresses electron flow, but enhances ionic flow.     

Perovskite SrFe1-xTixO3-δ (x < = 0.1) cathode for low temperature solid oxide fuel cell

Stable and compatible cathode materials are a key factor for realizing the low-temperature (LT, ≤600?°C) operation and practical implementations of solid oxide fuel cells (SOFCs). In this study, perovskite oxides SrFe_1-xTi_xO_3-δ (x?< = 0.1), with various ratios of Ti doping, are prepared by a sol-gel method for cathode material for LT-SOFCs. The structure, morphology and thermo-gravimetric characteristics of the resultant SFT powders are investigated. It is found that the Ti is successfully doped into SrFeO_3-δ to form a single phase cubic perovskite structure and crystal structure of SFT shows better stability than SrFeO_3-δ. The dc electrical conductivity and electrochemical properties of SFT are measured and analysed by four-probe and electrochemical impedance spectra (EIS) measurements, respectively. The obtained SFT exhibits a very low polarization resistance (R_p), .01 Ωcm² at 600?C. The SFT powders using as cathode in fuel cell devices, exhibit maximum power density of 551?mW?cm^?2 with open circuit voltage (OCV) of 1.15?V at 600?C. The good performance of the SFT cathode indicates a high rate of oxygen diffusion through the material at cathode. By enabling operation at low temperatures, SFT cathodes may result in a practical implementation of SOFCs.     

The influence of activated carbon as an additive in anode materials for low temperature solid oxide fuel cells

The effects of activated carbon (AC) as an additive in multi-oxide nano composite LiNiCuZn–O for application as anode in solid oxide fuel cell (SOFC) is reported. The composite was synthesized using solid state reactions method with varying content of AC in range 0.1%–0.9% for use as anode in the cell. The cell was composed of the synthesized composite as anode, LiNiCuZn–O as cathode and Samaria doped ceria (SDC) as electrolyte. The prepared composites were characterized for morphology and crystal structure by scanning electron microscope (SEM) and x-ray diffraction (XRD) respectively. Furthermore, the crystallite sizes of LiNiCuZn–O and LiNiCuZn–O with AC as an additive have been found in the range from 50 nm to 70 nm. The prepared composite materials were observed porous and the porosity of the sample having 0.5% additive was found highest. The conductivity and power density of the SOFC were studied at temperature of 600 °C. The maximum value of conductivity was found as 4.79 S/cm for the composite containing 0.5% AC as measured by using 4-probe method. The maximum value of power density of the fuel cell with anode comprising of 0.5% AC along with the mentioned cathode and the electrolyte was 455 mW/cm². Therefore, out of the compositions studied, the composite comprising of LiNiCuZn–O with 0.5% AC offered best performance for anode in the cell. This oxide composite is reported as a potential candidate for use as anode in low temperature SOFCs.     

Static stress analysis of carbon nano-tube reinforced composite (CNTRC) cylinder under non-axisymmetric thermo-mechanical loads and uniform electro-magnetic fields

Static stresses analysis of carbon nano-tube reinforced composite (CNTRC) cylinder made of poly-vinylidene fluoride (PVDF) is investigated in this study. Non-axisymmetric thermo-mechanical loads are applied on cylinder in presence of uniform longitudinal magnetic field and radial electric field. The surrounded elastic medium is modeled by Pasternak foundation because of its advantages to the Winkler type. Distribution of radial, circumferential and effective stresses, temperature field and electric displacements in CNTRC cylinder are determined based on Mori–Tanaka theory. The detailed parametric study is conducted, focusing on the remarkable effects of magnetic field intensity, elastic medium, angle orientation and volume fraction of carbon nano-tubes (CNTs) on distribution of effective stress. Results demonstrated that fatigue life of CNTRC cylinder will be significantly dependent on magnetic intensity, angle orientation and volume fraction of CNTs. Results of this research can be used for optimum design of thick-walled cylinders under multi-physical fields.     

Effect of strontium and zirconium doped barium cerate on the performance of proton ceramic electrolyser cell for syngas production from carbon dioxide and steam

Syngas has been produced from carbon dioxide (CO₂) and steam using a proton ceramic electrolyser cell. Proton-conducting electrolytes which exhibit high conductivity can suffer from low chemical stability. In this study, to optimize both proton conductivity and chemical stability, barium cerate and doped barium cerate are synthesized using solid state reaction method: BaCeO₃ (BC), Ba_0.6Sr_0.4CeO_3-α (BSC), Ba_0.6Sr_0.4Ce_0.9Y_0.1O_3-α (BSCY), and BaCe_0.6Zr_0.4O_3-α (BCZ). The BC, BSC, and BSCY are calcined at 1100 °C for 2 h and BCZ is calcined at 1300 °C for 12 h, respectively. All samples exhibit 100% perovskite and crystallite sizes equal 37.05, 28.46, 23.65 and 17.46 nm for BC, BSC, BSCY and BCZ, respectively. Proton conductivity during steam electrolysis as well as catalytic activity toward the reverse water gas shift reaction (RWGS) is tested between 400 and 800 °C. The conductivity increases with temperature and the values of activation energy of conduction are 64.69, 100.80, 103.78 and 108.12 kJ mol⁻¹ for BSCY, BC, BSC, and BCZ, respectively. It is found that although BCZ exhibits relatively low conductivity, the material provides the highest CO yield at 550–800 °C, followed by BSCY, BSC, and BC, correlating to the crystallite size and BET surface area of the samples. Catalytic activity toward RWGS of composited Cu and electrolytes is also measured. Additional Cu (60 wt%) significantly increases catalytic activity. The CO yield increases from 3.01% (BCZ) to 43.60% (Cu/BCZ) at 600 °C and CO can be produced at temperature below 400 °C. There is no impurity phase detected in BCZ sample after exposure to CO₂-containing gas mixture (600 °C for 5 h) while CeO₂ phase is detected in BSC and BSCY and both CeO₂ and BaO are observed in BC sample.     

Self-assembled cubic-hexagonal perovskite nanocomposite as intermediate-temperature solid oxide fuel cell cathode

Self-assembly is an emerging strategy for preparing composite cathodes with good oxygen electrochemical reduction activity and congenital chemical compatibility for intermediate-temperature solid oxide fuel cell (IT-SOFC). Here we report that a self-assembled BaCo_0.6Zr_0.4O_3-δ (BZC-BC) nanocomposite is prepared through one-pot glycine-nitrate process and exhibits high cathode performance. The BZC-BC nanocomposite is composed of 62 mol% cubic perovskite BaZr_0.82Co_0.18O_3-δ (BZC) as an ionic conductor and 38 mol% hexagonal perovskite BaCo_0.96Zr_0.04O_2.6+δ (12H-BC) as a mixed ionic and electronic conductor. The BZC-BC nanocomposite has the pomegranate-like particles aggregated with a larger number of nanoparticles (50-100 nm) which greatly enlarge the three-phase boundary sites. The BZC-BC nanocomposite exhibits a thermal expansion coefficient of 12.89 × 10⁻⁶ K⁻¹ well-matched with that of Ce_0.8Gd_0.2O_3-δ (12.84 × 10⁻⁶ K⁻¹) electrolyte. The high electro-catalytic activity of BZC-BC nanocomposite cathode for oxygen reduction is reflected by the low polarization resistances of oxygen ions incorporation at cathode/electrolyte interface (0.02823 Ω cm²), oxygen species diffusion (0.03702 Ω cm²) and oxygen adsorptive dissociation (0.07609 Ω cm²) at 700 °C. The single cell with BZC-BC nanocomposite cathode achieves the maximum power density of 1094 mW cm⁻² at 650 °C and shows good stability under 25 h run.     

Thermal,mechanical and structural investigation of copolyimide–silica hybrids containing phosphine oxide

In this study, a novel hybrid copolyimide was synthesized from copolyamic acid solutions (PAAs) obtained by the reaction between bis(3-aminophenoxy-4-phenyl)phenylphosphine oxide (m-BAPPO), 3,3′-diaminodiphenyl sulfone (DDS) and 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), followed by thermal imidization. Hybrid materials containing 5% SiO₂ were synthesized by sol–gel technique. The polyimide–silica hybrids were characterized by Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Thermogravimetric analysis showed that the weight loss of hybrids is shifted to the higher temperature compared to the neat copolyimide. The contact angle measurements confirmed the hydrophobic surface of hybrids. Moreover, the gas permeability measurements were also done to take a step for forthcoming gas separation studies. The tensile modulus and strength of the copolyimides are good.     

Sag in drying coatings: Prediction and real time measurement with particle tracking

Sag is a coating phenomenon characterized by gravity-driven flow after deposition; excessive amounts of sag can lead to coating defects. In this work, a new method for evaluating and quantifying sag is investigated. The motion of micron-sized Lycopodium spores on an inclined coating surface is tracked during drying, and the resulting surface velocity data is used to determine sag length. This in situ particle tracking method is minimally invasive and permits real time measurements. Measured sag lengths and real time surface velocities in aqueous polyvinyl alcohol solution coatings compare well with a theoretical model. The model is also used to develop a predictive sag regime map, which anticipates the extent of sag given coating properties and process-specific parameters. This map also identifies viable processing windows and aids in intelligent coating design given specific process constraints. The predictions of the sag regime map are compared against experimental sag results from polyvinyl alcohol solution coatings as well as four commercial latex paints, revealing good agreement for coatings with Newtonian or ‘Newtonian-like’ rheologies.     

Plasmonic Bi nanoparticle decorated BiVO4/rGO as an efficient photoanode for photoelectrochemical water splitting

We report the application of plasmonic Bi nanoparticles supported rGO/BiVO₄ anode for photoelectrochemical (PEC) water splitting. Nearly, 2.5 times higher activity was observed for Bi-rGO/BiVO₄ composite than pristine BiVO₄. Typical results indicated that Bi-rGO/BiVO₄ exhibits the highest current density of 6.05 mA/cm² at 1.23 V, whereas Bi–BiVO₄ showed the current density of only 3.56 mA/cm². This enhancement in PEC activity on introduction of Bi-rGO is due to the surface plasmonic behavior of BiNPs, which improves the absorption of radiation thereby reduces the charge recombination. Further, the composite electrode showed good solar to hydrogen conversion efficiency, appreciable incident photon-to-current efficiency and low charge transfer resistance. Hence, Bi-rGO/BiVO₄ provides an opportunity to realize PEC water splitting.     

Origin of the temperature stability of dielectric constant in CaCu3Ti4O12

The temperature and dc bias stability of the dielectric constant and loss tangent of CaCu₃Ti₄O₁₂ samples sintered under different oxygen atmospheres are discussed. The results suggest that the metal-oxygen vacancy related defects not only provide the charge carriers for the conduction (defect doping) but also contribute to the huge permittivity in the way of defect dipoles repositioning under charge carrier hopping. The charge localization in a specific copper-oxygen vacancy defect complex is the reason of the huge and stable permittivity and low dielectric loss in the middle temperature range, 90 K-200 K (20 Hz), while the implementation of the large barrier layer height needs a contribution by the titanium oxygen vacancy related trap charges in the grain boundaries, which also lead to a second permittivity stable range in a higher temperature range 200 K–300 K.