Proton-exchange membrane fuel cell design for in-situ depth-sensitive X-ray absorption spectroscopy

We have built a proton exchange membrane hydrogen fuel cell optimized for angle-resolved X-ray absorption spectroscopy. This cell allows in-situ fluorescence measurements during electrochemical operation with minimal trade-offs in cell performance while reaching automotive current densities. The fluorescence signal can be collected from wide angles to extract depth information from the probed atomic species such as Pt, Co, and Ni, crucial to highly efficient FC. This cell is designed to assess the connection between the ionic drag/diffusion and the performance loss by following the real-time movement of the species through the membrane electrode assembly

A comparison of rotating disc electrode, floating electrode technique and membrane electrode assembly measurements for catalyst testing

International audienceThe development of new catalysts for low temperature fuel cells requires accurate characterization techniques to evaluate their performance. As initially only small amounts of catalyst are available, preliminary screening must rely on suitable test methods. In this work, using a carbon supported platinum benchmark catalyst, the rotating disc electrode (RDE) technique was revisited in order to develop a detailed testing protocol leading to comparable results between different laboratories. The RDE results were validated by comparison with data measured both in proton exchange membrane single cells and via the relatively new floating electrode technique. This method can be operated with small amounts of catalyst but does not suffer from low limiting currents and allows prediction of high current capability of newly developed catalysts. Different durability testing protocols were tested with all three methods. Such protocols need to be able to introduce changes in the reference catalyst, but must not be too harsh as otherwise they cannot be applied to alloy catalysts. In all protocols an upper potential limit of 0.925 V was used, as this produced degradation in the chosen benchmark catalyst, but still represents realistic conditions for alloy catalysts

The origin of high activity but low CO₂ selectivity on binary PtSn in the direct ethanol fuel cell

Combined electrochemical in situ FTIR and DFT study provides an insight into ethanol fuel cell catalysis on the most active binary catalyst, PtSn, at the atomic and molecular levels.</p

Effects of PEMFC Operational History under Dry/Wet Conditions on Additional Voltage Losses due to Ionomer Migration

Over its lifetime in a fuel cell electric vehicle, a polymer electrolyte membrane fuel cell inevitably suffers from certain duration of dry operational conditions, where significant performance losses of the fuel cell take place. In this study, we investigate the activity changes of the fuel cell after a prolonged degradation protocol under dry operational condition, followed by various recovery procedures under wet conditions. The utilization of diluted air on the cathode side is found to be advantageous for the recovery due to the superior heat and water management. This more efficient recovery protocol allows the deconvolution of reversible and irreversible voltages losses after dry operations. A subsequent mechanistic study reveals an irreversible decrease of the effective ionomer coverage on the catalyst particles, while the proton conductivity of the catalyst layer drops. These observations point towards ionomer structural changes caused by the dry conditions. This is confirmed by post-mortem analysis via scanning electron microscope, showing clearly that ionomer redistributes and migrates, an additional mechanism which leads to the performance losses. Overall, the degradation mechanisms seem to be mitigated by higher ionomer content in the catalyst layer, while the investigated surface modification of carbon support shows minor sensitivities.ISSN:0013-4651ISSN:1945-711

High loading of single atomic iron sites in Fe–NC oxygen reduction catalysts for proton exchange membrane fuel cells

International audienc

Assessing Utilization Boundaries for Pt-based Catalysts in an Operating PEMFC

Octahedra (oh) PtNiX/C catalysts have attracted attention as cathode catalysts for proton-exchange membrane fuel cells (PEMFCs) due to their exceptional catalytic activities toward the oxygen reduction reaction. Here, we investigate the degradation dynamics of oh-PtNiIr in fuel cell conditions by operando X-ray diffraction (XRD). Two XRD-coupled square-wave accelerated stress tests (0.6 to 0.95) V and (0.7 to 0.95) V (where V is the cell voltage) confirm that, when fixing the upper limit, the dissolution and overall degradation strongly depend on the lower potential limit. By directly observing the extent of metal oxidation during potential cycling, we link the alloy redox dynamics to the stability. The studied catalysts\u27 stability is proportional to both the extent of metal oxidation and, more interestingly, the degree of reduction. Comparing a benchmark Pt catalyst with oh-PtNiIr allows for associating the differences between oxidation and reduction potentials and the optimal usage window for each class of catalysts. This relatively simple method can be employed to find the operation boundaries of the PEMFC to minimize the degradation of a large class of Pt-based catalysts without time-consuming stress tests

Temperature-Driven Dissolution of Nanoalloyed Catalyst During Ink Preparation and Membrane Electrode Assembly Fabrication

Platinum (Pt) alloys are excellent oxygen-reduction catalysts used in proton exchange membrane fuel cells, yet their effective integration poses challenges. Through in-situ X-ray diffraction, we investigate the compositional changes during the ink preparation of PtCo and PtNi catalysts and reveal that dissolution is primarily driven by temperature. Comparisons with conventional catalyst-coated membrane (CCM) fabrication methods highlight structural transformations during hot-pressing. Paving the way for advancements in sustainable energy technologies, our findings emphasize the essential need for fundamental knowledge of ink-making and CCM fabrication to unlock Pt-alloy catalyst potential for hydrogen fuel cells. In addition to the academic community, the industry shall benefit from this precise and easy-to-employ methodology

Differences and similarities in endothelial and angiogenic profiles of preeclampsia and COVID-19 in pregnancy.

Background: COVID-19 presents a spectrum of signs and symptoms in pregnant women that might resemble preeclampsia. Differentiation between severe COVID-19 and preeclampsia is difficult in some cases. Objective: To study biomarkers of endothelial damage, coagulation, innate immune response, and angiogenesis in preeclampsia and COVID-19 in pregnancy in addition to in vitro alterations in endothelial cells exposed to sera from pregnant women with preeclampsia and COVID-19. Study design: Plasma and sera samples were obtained from pregnant women with COVID-19 infection classified into mild (n=10) or severe (n=9) and from women with normotensive pregnancies as controls (n=10) and patients with preeclampsia (n=13). A panel of plasmatic biomarkers was assessed, including vascular cell adhesion molecule-1, soluble tumor necrosis factor-receptor I, heparan sulfate, von Willebrand factor antigen (activity and multimeric pattern), α2-antiplasmin, C5b9, neutrophil extracellular traps, placental growth factor, soluble fms-like tyrosine kinase-1, and angiopoietin 2. In addition, microvascular endothelial cells were exposed to patients' sera, and changes in the cell expression of intercellular adhesion molecule 1 on cell membranes and von Willebrand factor release to the extracellular matrix were evaluated through immunofluorescence. Changes in inflammation cell signaling pathways were also assessed by of p38 mitogen-activated protein kinase phosphorylation. Statistical analysis included univariate and multivariate methods. Results: Biomarker profiles of patients with mild COVID-19 were similar to those of controls. Both preeclampsia and severe COVID-19 showed significant alterations in most circulating biomarkers with distinctive profiles. Whereas severe COVID-19 exhibited higher concentrations of vascular cell adhesion molecule-1, soluble tumor necrosis factor-α receptor I, heparan sulfate, von Willebrand factor antigen, and neutrophil extracellular traps, with a significant reduction of placental growth factor compared with controls, preeclampsia presented a marked increase in vascular cell adhesion molecule-1 and soluble tumor necrosis factor-α receptor I (significantly increased compared with controls and patients with severe COVID-19), with a striking reduction in von Willebrand factor antigen, von Willebrand factor activity, and α2-antiplasmin. As expected, reduced placental growth factor, increased soluble fms-like tyrosine kinase-1 and angiopoietin 2, and a very high soluble fms-like tyrosine kinase-1 to placental growth factor ratio were also observed in preeclampsia. In addition, a significant increase in C5b9 and neutrophil extracellular traps was also detected in preeclampsia compared with controls. Principal component analysis demonstrated a clear separation between patients with preeclampsia and the other groups (first and second components explained 42.2% and 13.5% of the variance), mainly differentiated by variables related to von Willebrand factor, soluble tumor necrosis factor-receptor I, heparan sulfate, and soluble fms-like tyrosine kinase-1. Von Willebrand factor multimeric analysis revealed the absence of von Willebrand factor high-molecular-weight multimers in preeclampsia (similar profile to von Willebrand disease type 2A), whereas in healthy pregnancies and COVID-19 patients, von Willebrand factor multimeric pattern was normal. Sera from both preeclampsia and severe COVID-19 patients induced an overexpression of intercellular adhesion molecule 1 and von Willebrand factor in endothelial cells in culture compared with controls. However, the effect of preeclampsia was less pronounced than the that of severe COVID-19. Immunoblots of lysates from endothelial cells exposed to mild and severe COVID-19 and preeclampsia sera showed an increase in p38 mitogen-activated protein kinase phosphorylation. Patients with severe COVID-19 and preeclampsia were statistically different from controls, suggesting that both severe COVID-19 and preeclampsia sera can activate inflammatory signaling pathways. Conclusion: Although similar in in vitro endothelial dysfunction, preeclampsia and severe COVID-19 exhibit distinctive profiles of circulating biomarkers related to endothelial damage, coagulopathy, and angiogenic imbalance that could aid in the differential diagnosis of these entities