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.     

Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

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.     

Diluted chemical bath deposition of CdZnS as prospective buffer layer in CIGS solar cell

In this study, dilute chemical bath deposition technique has been used to deposit CdZnS thin films on soda-lime glass substrates. The structural, morphological, optoelectronic properties of as-grown films have been investigated as a function of different Zn²⁺ precursor concentrations. The X-ray diffractogram of CdS thin-film reveals a peak corresponding to (002) plane with wurtzite structure, and the peak shift has been observed with the increase of the Zn²⁺ concentration upon formation of CdZnS thin film. From morphological studies, it has been revealed that the diluted chemical bath deposition technique provides homogeneous distribution of film on the substrate even at a lower concentration of Zn²⁺. Optical characterization has shown that the transparency of the film is influenced by Zn²⁺ concentration and when the Zn²⁺ concentration is varied from 0 M to 0.0256 M, bandgap values of resulting films range from 2.42 eV to 3.90 eV while. Furthermore, electrical properties have shown that with increasing zinc concentration the resistivity of the film increases. Finally, numerical simulation validates and suggests that CdZnS buffer layer with composition of 0.0032 M Zn²⁺ concentration would be a promising candidate in CIGS solar cell.     

Magnetic properties,phase evolution,hollow structure and biomedical application of hematite (α-Fe2O3) and QUAIPH

We investigate synthesis, phase evolution, hollow and porous structure and magnetic properties of quasi-amorphous intermediate phase (QUAIPH) and hematite (α-Fe₂O₃) nanostructure synthesized by annealing of akaganeite (β-FeOOH) nanorods. It is found that the annealing temperature determines the phase composition of the products, the crystal structure/size dictates the magnetic properties whereas the final nanorod morphology is determined by the starting material. Annealing of β-FeOOH at ～300 °C resulted in the formation of hollow QUAIPH nanorods. The synthesized material shows low-cytotoxicity, superparamagnetism and good transverse relaxivity, which is rarely reported for QUAIPH. The QUAIPH nanorods started to transform to porous hematite nanostructures at ～350 °C and phase transformation was completed at 600 °C. During the annealing, the crystal structure changed from monoclinic (akaganeite) to quasi-amorphous and rhombohedral (hematite). Unusually, the crystallite size first decreased (akaganeite → QUAIPH) and then increased (QUAIPH → hematite) during annealing whereas the nanorods retained particle shape. The magnetic properties of the samples changed from antiferromagnetic (akaganeite) to superparamagnetic with blocking temperature T_B = 84 K (QUAIPH) and finally to weak-ferromagnetic with the Morin transition at T_M = 244 K and high coercivity H_C = 1652 Oe (hematite). The low-cytotoxicity and MRI relaxivity (r₂ = 5.80 mM^?1 s^?1 (akaganeite), r₂ = 4.31 mM^?1 s^?1 (QUAIPH) and r₂ = 5.17 mM^?1 s^?1 (hematite)) reveal potential for biomedical applications.     

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.     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.