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.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

In vivo Kinetic Biodistribution of Nano‐Sized Outer Membrane Vesicles Derived from Bacteria

Evaluation of kinetic distribution and behaviors of nanoparticles in vivo provides crucial clues into their roles in living organisms. Extracellular vesicles are evolutionary conserved nanoparticles, known to play important biological functions in intercellular, inter‐species, and inter‐kingdom communication. In this study, the first kinetic analysis of the biodistribution of outer membrane vesicles (OMVs)—bacterial extracellular vesicles—with immune‐modulatory functions is performed. OMVs, injected intraperitoneally, spread to the whole mouse body and accumulate in the liver, lung, spleen, and kidney within 3 h of administration. As an early systemic inflammation response, increased levels of TNF‐α and IL‐6 are observed in serum and bronchoalveolar lavage fluid. In addition, the number of leukocytes and platelets in the blood is decreased. OMVs and cytokine concentrations, as well as body temperature are gradually decreased 6 h after OMV injection, in concomitance with the formation of eye exudates, and of an increase in ICAM‐1 levels in the lung. Following OMV elimination, most of the inflammatory signs are reverted, 12 h post‐injection. However, leukocytes in bronchoalveolar lavage fluid are increased as a late reaction. Taken together, these results suggest that OMVs are effective mediators of long distance communication in vivo.     

Polyetherimide-LaNi5 composite films for hydrogen storage applications

This study investigates the preparation of polyetherimide (PEI) – LaNi₅ composites films for hydrogen storage. Prior to the polymer addition, LaNi₅ was ball-milled at different conditions (250, 350, and 450 RPM) and annealed at 500 °C for 1 h under vacuum. The composites were produced with BM-LaNi₅-350 (PEI/LaNi₅-350) and annealed BM-LaNi₅-350 (PEI/LaNi₅-350-TT). Membranes were successfully produced through solvent casting assisted by an ultrasonic bath. The particles dispersion and the film morphology did not change after hydrogenation cycles. In the H₂ sorption experiments at 43 °C and 20 bar, the films stored H₂ without incubation time; both samples reached a capacity of ~0.6 wt%. The H₂ sorption kinetics of PEI/LaNi₅-350 was comparable to that of BM-LaNi₅-350, whereas PEI/LaNi₅-350-TT presented significantly slower kinetics. LaNi₅ oxidation was hindered by PEI, showing that it can be explored to improve metal hydrides air resistance. The results demonstrated that PEI films filled with LaNi₅ are promising materials for hydrogen storage.     

Design and synthesis of side-chain optimized poly(2,6-dimethyl-1,4-phenylene oxide)-g-poly(styrene sulfonic acid) as proton exchange membrane for fuel cell applications: Balancing the water-resistance and the sulfonation degree

Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g^?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm^?1 at 40 °C and 45.5 mS cm^?1 at 95 °C, respectively.     

Investigation on sulphonated zinc oxide nanorod incorporated sulphonated poly (1,4-phenylene ether ether sulfone) nanocomposite membranes for improved performance of microbial fuel cell

Hydrothermally prepared zinc oxide nanorods are sulphonated (S–ZnO NR) and incorporated into 15% Sulphonated Poly (1,4-Phenylene Ether Ether Sulfone) (SPEES) to improve the hydrophilicity, water uptake and ion transfer capacity. Water uptake and ion transfer capacity increased to 34.6 ± 0.6% and 2.0 ± 0.05 meq g^?1 from 29.8 ± 0.3% and 1.4 ± 0.04 meq g^?1 by adding 7.5 wt% S–ZnO NR to SPEES. Morphological studies show the prepared S–ZnO NR is well dispersed in the polymer matrix. SPEES +7.5 wt% S–ZnO NR membrane exhibits optimum performance after three-weeks of continual operation in a fabricated microbial fuel cell (MFC) to produce a maximum power density of 142 ± 1.2 mW m^?2 with a reduced biofilm compared to plain SPEES (59 ± 0.8 mW m^?2), unsulphonated filler incorporated SPEES (SPEES + 7.5 wt% ZnO, 68 ± 1.1 mW m^?2) and Nafion (130 ± 1.5 mW m^?2) thereby suggesting its suitability as a sustainable and improved cation exchange membrane (CEM) for MFCs.     

Fabrication of BSCF-based mixed ionic-electronic conducting membrane by electrophoretic deposition for oxygen separation application

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF), which exhibits a high mixed oxide ionic-electronic conduction, was used for the fabrication of an oxygen separation membrane. An asymmetric structure, which was a thin and dense BSCF membrane layer supported on a porous BSCF substrate, was fabricated by the electrophoretic deposition method (EPD). Porous BSCF supports were prepared by the uniaxial pressing method using a powder mixture with BSCF and starch as the pore-forming agent (0–50 wt.%). The sintering behaviors of the porous support and the thin layer were separately characterized by dilatometry to determine the co-fired temperature at which cracking did not occur. A crack-free and thin dense membrane layer, which had about a 15 μm thickness and >95% relative density, was obtained after optimizing the processes of EPD and sintering. The dense/porous interface was well-bonded and the oxygen permeation flux was 2.5 ml (STP) min⁻¹ cm^-2 at 850 °C.