Completely eliminating the metal barrier cracks on Nafion for suppressing methanol crossover with anodic aluminum oxide substrates

Methanol crossover is one of the main challenges for direct methanol fuel cells (DMFCs). Depositing a metal barrier on Nafion can reduce the crossover but usually faces the metal cracking issues. This study presents a new composite membrane in which an anodic aluminum oxide (AAO) substrate is impregnated with a Nafion solution and then coated with a layer of Au. The AAO/Nafion/Au composite membrane shows an ideal metal crack-free surface. Higher and more stable voltage has been achieved for the cell with the membrane, indicating an effectively suppressed methanol-crossover. Results reveal that there is a tradeoff between suppressing the methanol crossover and increasing the ion transmission. By optimizing the membrane, it can not only suppress the methanol crossover but also enhance the output performance of DMFCs. The current density and power density of the cells can be enhanced by 59% and 52.85%, respectively, compared to the cell with a commercial Nafion 117. Overall, this work provides a new approach to designing crack-free membranes for DMFCs.     

Electrochemical performance of spherical Li-rich LMNCO cathode materials prepared using a two-step spray-drying method

In this study we synthesized Li-rich Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ (LMNCO) as a composite cathode material through a two-step spray-drying method, using transition metal (TM) acetates and citric acid (CA, as a chelating agent) at various molar ratios and then calcining at various temperatures for various periods of time. This two-step spray-drying method created hierarchical nano/micro-sphere structures of the LMNCO cathode material. The LMNCO cathode exhibited the best electrochemical performance when synthesized with a TM:CA ratio of 3:2, a calcination temperature of 900 °C, and a calcination time of 5 h. This as-prepared LMNCO composite was then modified with polyimide (PI) at various weight ratios (PI/LMNCO = 0.5, 1.0, and 1.5 wt%) to improve its electrochemical properties. Among the various structures, the LMNCO cathode material coated with 1.0 wt% of PI at a layer thickness of approximately 1.88 nm achieved the best initial discharge capacities. This modified electrode also displayed enhanced cycle stability, with over 93.3 and 87.9% of the capacity retained after 30 cycles at 0.1C and 100 cycles at 1C, respectively. In comparison, the capacity retention of the unmodified LMNCO electrode measured under the same conditions was no more than 91.3% at 0.1C and 70.1% at 1C. Thus, surface modification with PI was an effective method for improving the coulombic efficiency, discharge capacity, and long-term cycling performance of the LMNCO cathode. Such PI-coated LMNCO composite cathode materials appear to be potential candidates for use in next-generation high-performance lithium-ion batteries.     

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.     

Controlled growth of Bi-Functional La doped CeO2 nanorods for photocatalytic H2 production and supercapacitor applications

The rapid increase in energy consumption has severely rehabilitated human life urging to develop reliable and environmental friendly energy storage devices. Target oriented, systematic approach has been adopted to synthesis La doped CeO₂ nanostructures with percentage as La_xCe_1-xO₂ (X = 0,1,3,5,7) for potential super capacitors applications. Morphological doping impact on H₂ production, electrochemical and optical properties are thoroughly investigated. XRD studies revealed the crystalline phase purity and attained approximately 35 nm average crystallite size. The SEM images exposed that primary morphology nano-particles has been tuned into nanorods by increasing the La concentration in CeO₂ with size range 40～60 nm. CV graphs depicted that the prepared electrodes obey the pseudo capacitive faradaic reactions behavior in nature. Maximum capacitance (925 F g^-1) has been achieved by La_0·05Ce_0·95O₂ which is better than numerous reported materials. The La_0·05Ce_0·95O₂ also exhibited excellent GCD stability with 87.8% retention exhibiting it suitability for supercapacitor applications. Furthermore, the La_0·05Ce_0·95O₂ showed the significantly higher H₂ (9 μmol h^?1g^?1) production rate as compared to undoped CeO₂ and La_0·01Ce_0·99O_2, La_0·03Ce_0·97O₂ samples. This higher production is attributed to the recombination rate and have strong substantial correlation with optical characteristics.     

Systematic analysis and multi-objective optimization of an integrated power and freshwater production cycle

This study represents the results of the analysis and optimization of an integrated system for cogenerating electricity and freshwater. This setup consists of a Solid Oxide Fuel cell (SOFC) for producing electricity. Unburned fuel of the SOFC is burned in the afterburner to increase the temperature of the SOFC's outlet gasses and operate a Gas turbine (GT) to produce additional power and operate the air compressor. At the bottom of this cycle, a combined setup of a Multi-Effect Desalination (MED) and Reverse Osmosis (RO) is considered to produce freshwater from the unused heat capacity of the GT's exhaust gasses. Also, a Stirling engine is used in the fuel supply line to increase the fuel's temperature. Using LNG and the Stirling engine will replace the fuel compressor with a pump which increases the system performance and eliminates the need for the expansion valve. To study the system performance a mathematical model is developed in Engineering Equation Solver (EES) program. Then, the system's simulated data from the EES has been sent to MATLAB to promote the best operating condition based on the optimization criteria. An energetic, exergetic, economic, and environmental analysis has been performed and a Non-dominated Sorting Genetic Algorithm (NSGA-II) is used to achieve the goal. The two-objective optimization is performed to maximize the exergetic efficiency of the proposed system while minimizing the system's total cost of production. This cost is a weighted distribution of the Levelized Cost of Electricity (LCOE) and Levelized Cost of freshwater (LCOW). The results showed that the exergetic and energetic efficiencies of the system can reach 73.5% and 69.06% at the optimum point. The total electricity production of the system is 99 MW. The production cost is 11.71 Cents/kWh, of which 1.04 Cents/kWh is emission-related and environmental taxes. The freshwater production rate is 42.44 kg/s which costs 4.38 USD/m³.     

Anodic corrosion of heteroatom doped graphene oxide supports and its influence on the electrocatalytic oxygen evolution reaction

Transition metal-based electrocatalysts supported on carbon substrates face the challenges of anodic corrosion of carbon during oxygen evolution reaction at high oxidation potential. The role of electrophilic functional groups (carbonyl, pyridinic, thiol, etc.) incorporated in graphene oxide has been studied towards the anodic corrosion resistance. Heteroatom functionalized carbon supports possess modified electronic properties, surface oxygen content, and hydrophilicity, which are crucial in governing electrochemical corrosion in the alkaline oxidative environment. Evidently, electron-withdrawing groups in NGO support (pyridinic, cyano, nitro, etc) and its lower oxygen content impart maximum corrosion resistance and anodic stability in comparison to the other sulfur-doped and co-doped graphene oxide support. In this report, we establish the baseline evaluation of carbon-supported OER electrocatalysts by a systematic analysis of activity and substrate corrosion resistance. The result of this study establishes the role of surface composition of the doped supports while for designing a stable, corrosion-resistant OER electrocatalyst.     

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.