525 research outputs found
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Evolution of Ionomer Morphology from Dispersion to Film: An in Situ X-ray Study
Ion-conducting polymers (ionomers) have been extensively studied in solution, as membranes and substrate-supported thin films for various electrochemical energy-conversion devices, including fuel cells and electrolyzers. Formation of an ionomer film from a solution, however, is not well understood, despite its importance for fabrication of electrodes in energy devices. Here, the evolution of the perfluorinated sulfonic acid morphology upon casting from a solution is observed using in situ grazing-incidence small- and wide-angle X-ray scattering. Aggregate interactions in dispersion directly impact the hydrophilic-domain network of the cast film and the onset of crystallization occurs simultaneously with the solution-to-film transition but continues to evolve on different time scales. In addition, confinement is shown to induce anisotropic morphology at multiple length scales. These results show promise for elucidating the role of casting parameters, drying protocols, and ionomer-solvent interactions in governing film morphology and open new avenues for establishing structure/processing/property relationships for ionomer films and modifying their transport functionality at catalytic interfaces
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Interplay between Swelling Kinetics and Nanostructure in Perfluorosulfonic Acid Thin-Films: Role of Hygrothermal Aging
Impacts of processing, storage, and operation on thin-film perfluorosulfonic acid (PFSA) ionomer coatings used in electrodes of electrochemical devices remains unestablished. In this work, alteration of structure-function relationship in ionomers is achieved via exposure to elevated temperature and humidity (hygrothermal aging). Findings reflect a strong inverse correlation between aging-induced ionomer thin-film domain orientation and water-transport kinetics evaluated from swelling. Impact of aging is shown to be more pronounced on platinum due to interactions with PFSA, as evidenced by greater increase in nanodomain orientation parallel to substrate accompanied by reduced water transport, in contrast to silicon support
Highly Permeable Perfluorinated Sulfonic Acid Ionomers for Improved Electrochemical Devices: Insights into Structure-Property Relationships.
Rapid improvements in polymer-electrolyte fuel-cell (PEFC) performance have been driven by the development of commercially available ion-conducting polymers (ionomers) that are employed as membranes and catalyst binders in membrane-electrode assemblies. Commercially available ionomers are based on a perfluorinated chemistry comprised of a polytetrafluoroethylene (PTFE) matrix that imparts low gas permeability and high mechanical strength but introduces significant mass-transport losses in the electrodes. These transport losses currently limit PEFC performance, especially for low Pt loadings. In this study, we present a novel ionomer incorporating a glassy amorphous matrix based on a perfluoro(2-methylene-4-methyl-1,3-dioxolane) (PFMMD) backbone. The novel backbone chemistry induces structural changes in the ionomer, restricting ionomer domain swelling under hydration while disrupting matrix crystallinity. These structural changes slightly reduce proton conductivity while significantly improving gas permeability. The performance implications of this trade-off are assessed, which reveal the potential for substantial performance improvement by incorporation of highly permeable ionomers as the functional catalyst binder. These results underscore the significance of tailoring material chemistry to specific device requirements, where ionomer chemistry should be rationally designed to match the local transport requirements of the device architecture
Structure-Property Relationship in Ionomer Membranes
Perfluorosulfonic acid (PFSA) ionomer membranes are ion-conducting polymers with high water sorption capacity and thermo-mechanical stability. The morphology of PFSA changes during sorption affecting the mechanical and physical properties of the membrane. In this work, we investigate the structure-property relationship in swollen PFSA membranes using three proposed nanostructural descriptions and determine Young\u27s modulus of the membrane at a wide range of temperatures (−20–85°C) and water volume fractions (0–0.5) for these configurations. Comparing the mechanics-based models with experimental data we propose that ion-rich water domains in PFSA membrane are spherical at low water content, spherical with connecting channels at intermediate water content and cylindrical at high water contents. Furthermore, our findings indicate that the scaling behavior for Young\u27s modulus of PFSA ionomers is similar to that of aerogels. This suggests, from a mechanics perspective, that aerogels and ionomers may have a similar interconnected porous nanostructure where some solid regions do not contribute to the mechanical load-bearing capacity
Aspects of Fatigue Failure Mechanisms in Polymer Fuel Cell Membranes
The swelling-driven fatigue behavior of polymer fuel cell membranes during relative humidity (RH) cycling is investigated. In particular, swelling-induced membrane stresses are obtained from a numerical model simulating fuel cell RH cycle tests, and compared to the lifetimes obtained experimentally from tests conducted in the absence of electrochemical effects. A strong correlation between the lifetimes of the membranes in the actual tests and model results is obtained. In general, higher RH (or swelling) amplitude results in larger stress amplitudes and shorter lifetime, that is, fewer cycles to failure. Tensile stresses are needed for forming local cavities in the membrane, which may eventually lead to craze formation. Cavitation is less likely to occur in compressed membrane at high humidities. The stress–lifetime plots for polymer fuel cell membranes exhibit similar features to those observed for other polymers. The crazing criterion for polymers suggests that craze initiation during RH cycling is more likely to occur in the low compression regions, such as under the channels, which is in agreement with experimental observations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1506–1517, 201
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Enhanced Charge Carrier Transport in 2D Perovskites by Incorporating Single-Walled Carbon Nanotubes or Graphene
Two-dimensional (2D) organic-inorganic (hybrid) perovskites are considered promising candidates to replace conventional three-dimensional (3D) perovskites for solar cell applications as they have good resistance against moisture and UV light. However, the use of 2D perovskite is associated with a significant decrease in power efficiency resulting from their low photogenerated charge carrier density and poor charge transport. To improve power efficiency in 2D perovskites, highly crystalline films (near-single-crystal quality) of 2D perovskite need to be synthesized where the alignment of the inorganic perovskite components is controlled to have vertical alignment with respect to the contacts to improve charge transport. In this work, we explored strategies to overcome this limitation by integrating 2D perovskite with single-walled carbon nanotubes or graphene to enable more efficient extraction of charge carriers toward electric contacts. Longer carrier lifetimes were achieved after the incorporation of the carbon nanostructures in the films, and at the cell level, power efficiency increased by 2-fold
Mechanical Behavior of Fuel Cell Membranes under Humidity Cycles and Effect of Swelling Anisotropy on the Fatigue Stresses
The mechanical response of proton exchange membranes in a fuel cell assembly is investigated under humidity cycles at a constant temperature (85°C). The behavior of the membrane under hydration–dehydration cycles is simulated by imposing a humidity gradient from the cathode to the anode. Linear elastic, plastic constitutive behavior with isotropic hardening and temperature and humidity dependent material properties are utilized in the simulations for the membrane. The evolution of the stresses and plastic deformation during the humidity cycles are determined using finite element analysis for two clamping methods and various levels of swelling anisotropy. The membrane response strongly depends on the swelling anisotropy where the stress amplitude decreases with increasing anisotropy. These results suggest that it may be possible to optimize a membrane with respect to swelling anisotropy to achieve better fatigue resistance, potentially enhancing the durability of fuel cell membranes
Mechanical Behavior of Fuel Cell Membranes under Humidity Cycles and Effect of Swelling Anisotropy on the Fatigue Stresses
The mechanical response of proton exchange membranes in a fuel cell assembly is investigated under humidity cycles at a constant temperature (85°C). The behavior of the membrane under hydration–dehydration cycles is simulated by imposing a humidity gradient from the cathode to the anode. Linear elastic, plastic constitutive behavior with isotropic hardening and temperature and humidity dependent material properties are utilized in the simulations for the membrane. The evolution of the stresses and plastic deformation during the humidity cycles are determined using finite element analysis for two clamping methods and various levels of swelling anisotropy. The membrane response strongly depends on the swelling anisotropy where the stress amplitude decreases with increasing anisotropy. These results suggest that it may be possible to optimize a membrane with respect to swelling anisotropy to achieve better fatigue resistance, potentially enhancing the durability of fuel cell membranes
Mechanical Response of Fuel Cell Membranes Subjected to a Hygro-Thermal Cycle
The mechanical response of fuel cell proton exchange membranes subjected to a single hygro-thermal duty cycle in a fuel cell assembly is investigated through numerical means. To this end, the behavior of the membrane with temperature and humidity dependent material properties is simulated under temperature and humidity loading and unloading conditions. The stress-evolution during a simplified operating cycle is determined using finite element analysis for two clamping methods and two alignments of the bipolar plates. It is shown that compressive, plastic deformation occurs during the hygro-thermal loading, resulting in tensile residual stresses after unloading. These residual in-plane stresses in the membrane may explain the occurrence of cracks and pinholes in the membrane under cyclic loading
Numerical Investigation of Mechanical Durability in Polymer Electrolyte Membrane Fuel Cells
The relationship between the mechanical behavior and water transport in the membrane electrode assembly (MEA) is numerically investigated. Swelling plays a key role in the mechanical response of the MEA during fuel cell operation because swelling can be directly linked to the development of stresses. Thus, in the model introduced here, the stresses and the water distribution are coupled. Two membranes are studied: unreinforced perfluorosulfonic acid (PFSA) and an experimental reinforced composite membrane. The results suggest that open-circuit voltage operations lead to a uniform distribution of stresses and plastic deformation, whereas under current-load operation, the stresses and the plastic deformation are generally lower and localized at the cathode side of the MEA. For the experimental reinforced membrane investigated, the in-plane swelling and, consequently, the stresses and plastic deformation are lower than in an unreinforced PFSA membrane. This reduction is a favorable outcome for improving durability. The model also suggests that the mechanical constraints due to the clamping of the cell may limit the swelling of the membrane and consequently change the water distribution
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