Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Investigation of La0.6Sr0.4Co1-xNixO3-δ (x=0, 0.2, 0.4, 0.6, 0.8) catalysts on solid oxide fuel cells anode for biogas dry reforming

The introduction of catalyst on anode of solid oxide fuel cell (SOFC) has been an effective way to alleviate the carbon deposition when utilizing biogas as the fuel. A series of La_0.6Sr_0.4Co_1-xNi_xO_3-δ (x = 0, 0.2, 0.4, 0.6, 0.8) oxides are synthesized by sol-gel method and used as catalysts precursors for biogas dry reforming. The phase structure of La_0.6Sr_0.4Co_1-xNi_xO_3-δ oxides before and after reduction are characterized by X-ray diffraction (XRD). The texture properties, carbon deposition, CH₄ and CO₂ conversion rate of La_0.6Sr_0.4Co_1-xNi_xO_3-δ catalysts are evaluated and compared. The peak power density of 739 mW cm^?2 is obtained by a commercial SOFC with La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst at 850 °C when using a mixture of CH₄: CO₂ = 2:1 as fuel. This shows a great improvement from the cell without catalyst for internal dry reforming, which is attributed to the formation of NiCo alloy active species after reduction in H₂ atmosphere. The results indicate the benefits of inhibiting the carbon deposition on Ni-based anode through introducing the La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst precursor. Additionally, the dry reforming technology will also help to convert part of the exhaust heat into chemical energy and improve the efficiency of SOFC system with biogas fuel.     

Activation of LSCF–YSZ interface by cobalt migration during electrolysis operation in solid oxide electrolysis cells

High-temperature water electrolysis through solid oxide electrolysis cells (SOEC) will play a key role in building a hydrogen economy in the future. However, the delamination between the air electrode and the electrolyte remains a critical issue to be addressed. Previously, it was hypothesized that Co migration may improve the catalytic activity of the SrZrO₃ second phase at the LSCF-YSZ interface, eventually leading to the delamination. In this work, the LSCF-YSZ interfaces sintered at different temperatures were examined in detail. The activation behaviors of the LSCF electrodes upon application with electrolysis current were characterized under different conditions. Further, samples containing purposely added SrZrO₃ interlayer with and without cobalt were fabricated and compared. The activation process is less significant for the sample with cobalt-added SrZrO₃ interlayer than the sample with pure SrZrO₃ layer, supporting the hypothesis that Co migration may lead to the activation behavior.     

Double emulsion (W/O/W) gel stabilised by polyglycerol polyricinoleate and calcium caseinate as mangiferin carrier: insights on formulation and stability properties

Mangiferin (MGF) is a phenolic compound isolated from mango, but its poor solubility significantly limits its use. In this study, MGF was embedded into the inner aqueous phase of W₁/O/W₂ emulsions. Firstly, the dissolution method of MGF was determined. MGF remained stable in solution with pH 13 at 30 min, and its solubility reached 10 mg mL⁻¹. When the pH of MGF solutions was adjusted from pH 13 to pH 6, MGF did not immediately crystallise, providing sufficient time to construct the MGF-loaded W₁/O/W₂ emulsions. Subsequently, the MGF-loaded W₁/O/W₂ emulsions were constructed using polyglycerol polyricinoleate (PGPR) and calcium caseinate (CAS). The formation and stability of the W₁/O/W₂ emulsions were investigated. The MGF-loaded W₁/O/W₂ emulsions stabilised with 1% PGPR and 1% – 3% CAS exhibited a low viscosity, limited loading capacity, and poor stability. Conversely, the MGF-loaded W₁/O/W₂ emulsions stabilised by 3%PGPR–3%CAS exhibited optimal loading capacity (encapsulation efficiency = 95.31% and loading efficiency = 0.91%) and stability, which was attributed to the fact that high viscosity and gel state retarded the migration of inner aqueous phase. These results indicated that the W₁/O/W₂ emulsions stabilised by PGPR and CAS may be a potential alternative for encapsulating mangiferin.     

Simulation of hydrogen and coal gas fueled flat-tubular solid oxide fuel cell (FT-SOFC)

Solid oxide fuel cells (SOFCs) are considered an important technology in terms of high efficiency and clean energy generation. Flat-tubular solid oxide fuel cell (FT-SOFC) which is a combination of tubular and planar cell geometries stands out with its performance values and low costs. In this study, the performance of an FT-SOFC is analyzed numerically by using finite element method-based design as a result of changing parameters by using different fuels which are pure hydrogen and coal gas with various proportions of CO. In addition, cell performance values for different temperatures were analyzed and interpreted. Analyzes have been performed by using COMSOL Multiphysics software. The rates of CO composition used are 10%, 20%, and 40%, respectively. In addition, the air was used as the oxidizer in all cases. The cell voltage and average cell power of the FT-SOFC were examined under the 800 °C operating condition. The maximum power value and current density value were obtained as 710 W/m² and 1420 A/m² for the flat-tubular cell, respectively. As a result of the study, it was observed that the maximum cell power densities increased with increasing temperature. Analysis results showed that FT-SOFCs have suitable properties for different fuel usage and different operating temperatures. High-performance values and design features in different operating conditions are expected to make FT-SOFC the focus of many studies in the future.     

Full AC analysis of value of DER to the grid and optimal DER scheduling

This paper presents part of the work ComEd and Quanta Technology have performed to quantify the locational and temporal value of DER to avoid distribution grid upgrade investments. It focuses on the formulation of a robust and efficient algorithm for DER optimal dispatch on a distribution feeder to mitigate the violation of current and voltage limits using the allocated cost of capacity and locational marginal value of real and reactive DER injection/withdrawal.     

Facile synthesis of MgO–Mg2SiO4 composite ceramics with high strength and low thermal conductivity

The recycling of solid waste is a win-win solution for humans and nature. For this purpose, magnesite tailings and silicon kerf waste were employed to prepare MgO–Mg₂SiO₄ composite ceramics by solid-state reaction synthesis in the present work. Then, effects of sintering temperature and raw material ratio on as-prepared ceramics were systematically studied. As-prepared ceramics showed improvement in their relative density (from 47.55%–68.12% to 90.96%–95.25%) and cold compressive strength (from 7.34–118.66 MPa to 303.39–546.65 MPa) with the increase in sintering temperature from 1300 to 1600 °C. In addition, it was found that Si promoted synthesis process of Mg₂SiO₄ phase through transient liquid phase sintering and Fe₂O₃ accelerated sintering process through activation sintering. Consequently, the presence of Mg₂SiO₄ phase effectively improved the density and strength of MgO–Mg₂SiO₄ composite ceramic, while reducing its thermal conductivity. This work provides a potential reutilization strategy for magnesite tailings, and as-prepared products are expected to be applied in fields of construction, metallurgy, and chemical industry.     

Sputtered Fe1·5CoNi0.5 coating: An improved protective coating for SOFC interconnect applications

In an attempt to optimize the properties of FeCoNi coating for planar solid oxide fuel cell (SOFC) interconnect application, the coating composition is modified by increasing the ratio of Fe/Ni. An Fe_1·5CoNi_0.5 (Fe:Co:Ni = 1.5:1:0.5, atomic ratio) metallic coating is fabricated on SUS 430 stainless steel by magnetron sputtering, followed by oxidation in air at 800°C. The Fe_1·5CoNi_0.5 coating is thermally converted to (Fe,Co,Ni)₃O₄ and (Fe,Co,Mn,Ni)₃O₄ without (Ni,Co)O particles. After oxidation for 1680 h, no further migration of Cr is detected in the thermally converted coating region. A low oxidation rate of 5.9 × 10^?14 g² cm^?4 s^?1 and area specific resistance of 12.64 mΩ·cm² is obtained for Fe_1·5CoNi_0.5 coated steels.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

Simultaneous fractionation of multiple classes of polyphenols from honeybush tea using solid-phase extraction

The structural diversity of polyphenols and the inherent limitations of current extraction techniques pose a challenge to extract polyphenols using a simple and green method. Hence, in this study, a method was developed to simultaneously fractionate multiple classes of polyphenols by only varying ethanol-water solutions. Honeybush tea, which is rich in polyphenols, was selected as a model for this study. Solvent extraction followed by solid-phase extraction (SPE) was developed to obtain a polyphenol-rich fraction from six honeybush samples. Based on a gradient elution programme (10%, 30%, 50%, 70% and 90% (v/v) ethanol-water solution) of SPE, the Strata X cartridge showed a better recovery of most targeted polyphenols under 0.9 mL of the drying volume and 1 mL min⁻¹ of the dispensing speed. The elution programme for fractionating most polyphenols was as follows: single elution with 50% ethanol, followed by twice elution with 70% ethanol. The antioxidant capacity was used to analyse the differences among the polyphenol-rich fractions from six honeybush samples. Principal component analysis (PCA) revealed that unfermented C. genistoides (GG) has the greatest antioxidant capacity among the honeybush species studied. Additionally, mangiferin, isomangiferin and vicenin-2 were the main contributors to the antioxidant capacity in six honeybush fractions according to the correlation study.