Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

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.     

One-step synthesis of Co2P/N-P co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts

Developing inexpensive and efficient electrocatalysts for hydrogen evolution reaction (HER) in both acidic and alkaline mediums is of great significance to the hydrogen energy industry. Hereby, we prepared a mixture of precursors with homogeneous composition by using the chelating ability of soybean protein isolate (C and N source) and phytic acid (dopant and phosphating agent) with cobalt ions, and achieved one-step synthesis and construction of Co₂P/N–P co-doped porous carbon composite by carbonization at 800 °C. The as-synthesized Co₂P/NPPC-800 electrocatalyst exhibits low HER overpotentials of 121 and 125 mV at 10 mA cm^?2 in 0.5 M H₂SO₄ and 1.0 M KOH, which are close to those of the commercial Pt/C catalyst. Additionally, the NPPC substrate surrounding the Co₂P could diminish the corrosion during the HER, and Co₂P/NPPC-800 displays good stability and durability. Furthermore, this work offers a convenient synthesis strategy for phosphide/doped porous carbon composites in other electrochemical energy technologies.     

A Ti3C2Tx-carbon black-acrylic epoxy coating for 304SS bipolar plates with enhanced corrosion resistant and conductivity

A conducting and anticorrosive coating is crucial for the application of metal bipolar plates (BP) in proton exchange membrane fuel cell (PEMFC). In this work, a Ti₃C₂T_x (T)-carbon black (C)-acrylic epoxy (AE) coating is prepared on 304 stainless steel (SS) with enhanced corrosion resistance and conductivity. The corrosion resistance of the T-C-AE coating is investigated in a 0.5 M H₂SO₄ solution as compared to the AE, T, and T-AE coatings. The T-C-AE coated 304SS exhibits the strongest corrosion resistance with the most positive corrosion potential and the lowest corrosion current density of 0.00673 μA cm^?2 in all the samples, while retaining intact and compact surface morphology with the lowest metal ion dissolution even after immersed for 720 h. The addition of Ti₃C₂T_x and carbon black into the AE matrix greatly decreases interfacial contact resistance (ICR), and the T-C-AE coating achieves a low ICR of 15.5 mΩ cm^?2 under 140 N cm^?2 compaction force. The excellent anticorrosion performance is mainly attributed to the physical barrier and the cathodic protection provided by the stacked Ti₃C₂T_x (MXene) nanosheets in the T-C-AE coating. This eco-friendly, conducting, and anticorrosive T-C-AE coating has a good application prospect on SS BP of PEMFC.     

Use of La2O3 with 8YSZ as thermal barrier coating and its effect on thermal cycle behavior,microstructure, mechanical properties and performance of diesel engine operated by hydrogen-algae biodiesel blend

In this present work, the effect of lanthanum oxides (La₂O₃) on the thermal cycle behavior of TBC coatings and mechanical properties such as adhesion strength and microhardness of 8% Yttria Stabilized Zirconia (8YSZ) TBCs were investigated. CoNiCrAlY and aluminium alloy (Al–13%Si) were used as bond coat and substrate materials. 8YSZ and different wt % of La₂O₃ (10, 20, and 30%) top coatings were applied using the atmospheric plasma spray (APS) method. The thermal cycling test for TBC coated samples were conducted at 800 °C in the electric furnace. The XRD pattern shows that the La₂O₃ doped 8YSZ material transformed to cubic pyrochloric structured La₂Zr₂O₇ during thermal cycling. Further, the Taguchi-based grey relation analysis (GRA) method was applied to optimize the TBC coating parameters to achieve better mechanical properties such as adhesion strength and microhardness. And the optimized La₂O₃/8YSZ TBC coating was coated on CRDI engine combustion chamber components. The engine was tested with microalgae biodiesel and hydrogen, and the results were promising for the TBC-coated engine. The engine performance increased while using La₂O₃/8YSZ coated components, and the emissions from engine exhaust gas such as CO, HC, and smoke reduced considerably. It was found that there was no separation crack and spallation of the coating layer in the microstructure. Ultimately, the microstructural analysis of the optimized TBC coated piston sample after 50 h of running in the diesel engine confirmed that the developed coating had a superior thermal insulation effect and longer life.     

Laser damage resistance of plasma-sprayed alumina and honeycomb skeleton/alumina composite ceramic coatings

Al₂O₃ and honeycomb skeleton-Al₂O₃ composite coatings on Titanium alloy (Ti–6Al–4V) were prepared by atmospheric plasma spraying. A laser ablation experiment on as-sprayed coatings was performed. In this paper, the laser damage resistance, microstructure, phase composition of Al₂O₃ coatings were examined. 3D Dimensional Confocal Microscopy, Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and Energy Dispersive Spectrometry (EDS) characterized the laser damage morphology, microstructure, phase composition, and element analysis, respectively. The influence of the honeycomb skeleton on the laser ablation damage on as-sprayed coatings was investigated by a comparative analysis of the laser damage morphology with different laser ablation times and gas flow. The results show that the honeycomb skeleton raises thermal conductivity and thermal diffusivity. Moreover, a “tower”-like dendrite was generated during the laser irradiation of the composite coating. The honeycomb skeleton refined the structure, suppressed crack propagation, and reduced the influence of gas flow on cracks. Under the same experimental laser ablation parameters, the laser damage area of the honeycomb skeleton-Al₂O₃ composite coating was smaller than that of the Al₂O₃ coating. It was demonstrated that the laser damage resistance of the honeycomb skeleton-Al₂O₃ composite coating was superior to that of the Al₂O₃ coating.     

Synthesis and characterization of ZnO NRs with spray coated GO for enhanced photocatalytic activity

Zinc oxide nanorods, ZnO NRs, were synthesized on a clean glass and coated with graphene oxide (GO) using spray coating method to enhance the photocatalytic activity in wastewater treatment. The ZnO NRs were synthesized using the solution process synthesis that was optimized using Taguchi method. Several synthesis parameters have been optimized and studied to determine the best synthesis parameter to grow ZnO NRs for the photodegradation of organic contaminants. Field emission scanning electron microscopy (FESEM) with EDX, X-ray diffraction (XRD), Raman, ultraviolet visible near-infrared (UV-VIS-NIR), and photoluminescence (PL) spectroscopies were used to investigate the structural and optical properties of the produced nanorods. FESEM images revealed the vertical growth of ZnO NRs as well as layers of GO covering the ZnO NRs' top surface. The Raman study demonstrates the combination peak of GO and ZnO, hence proving the GO layer's successful coating. After the GO coating, decrease in the bandgap of the synthesized photocatalyst was detected by PL and UV–Vis absorption measurements. Under UVC exposure with treatment time of 6 h, the degradation of MB with ZnO NRs/GO photocatalyst reached a degradation percentage of 97.86%, which is greater than the degradation percentage achieved using pristine ZnO NRs, which is 93.28%. The results validated that the coating of GO enhances the photocatalytic activity of the host material, ZnO NRs.     

Development and characterisation of microporous biomimetic scaffolds loaded with magnetic nanoparticles as bone repairing material

Fine-tuning of the scaffolds structural features for bone tissue engineering can be an efficient approach to regulate the specific response of the osteoblasts. Here, we loaded magnetic nanoparticles aka superparamagnetic iron oxide nanoparticles (SPIONs) into 3D composite scaffolds based on biological macromolecules (chitosan, collagen, hyaluronic acid) and calcium phosphates for potential applications in bone regeneration, using a biomimetic approach. We assessed the effects of organic (chitosan/collagen/hyaluronic acid) and inorganic (calcium phosphates, SPIONs) phase over the final features of the magnetic scaffolds (MS). Mechanical properties, magnetic susceptibility and biological fluids retention are strongly dependent on the final composition of MS and within the recommended range for application in bone regeneration. The MS architecture/pore size can be made bespoken through changes of the final organic/inorganic ratio. The scaffolds undertake mild degradation as the presence of inorganic components hinders the enzyme catalytic activity. In vitro studies indicated that osteoblasts (SaOS-2) on MS9 had similar cell behaviour activity in comparison with the TCP control. In vivo data showed an evident development of integration and resorption of the MS composites with low inflammation activity. Current findings suggest that the combination of SPIONs into 3D composite scaffolds can be a promising toolkit for bone regeneration.     

Synthesis,microstructures, and corrosion behaviors of multi-components rare-earth silicates

Multi-components and equimolar rare earth monosilicates, (Y_1/3Dy_1/3Er_1/3)₂SiO₅, (Y_1/3Dy_1/3Lu_1/3)₂SiO₅, (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅, were prepared by solid-state reactions and the following hot-pressing. Dense microstructures with uniform elemental distributions were obtained for all samples. These investigated multi-components monosilicates exhibit low thermal conductivities and similar coefficients of thermal expansion with SiC. Moreover, they exhibit high corrosion resistances in 1400 °C water vapor, especially, four-components (Y_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ and (Yb_1/4Dy_1/4Ho_1/4Er_1/4)₂SiO₅ experienced almost invariable weights after small weight losses during the initial 0.5 h. All those results indicate that multi-components rare earth monosilicates are promising candidates of environmental barrier coatings for SiC/SiC composites.