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

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

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

Morphology of supported polymer electrolyte ultra-thin films: a numerical study

Morphology of polymer electrolytes membranes (PEM), e.g., Nafion, inside PEM fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be found as an ultra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films has not been sufficiently explored yet. Here, we report about Molecular Dynamics simulation investigation of the substrate effects on the ionomer ultra-thin film morphology at different hydration levels. We use a mean-field-like model we introduced in previous publications for the interaction of the hydrated Nafion ionomer with a substrate, characterized by a tunable degree of hydrophilicity. We show that the affinity of the substrate with water plays a crucial role in the molecular rearrangement of the ionomer film, resulting in completely different morphologies. Detailed structural description in different regions of the film shows evidences of strongly heterogeneous behavior. A qualitative discussion of the implications of our observations on the PEMFC catalyst layer performance is finally proposed

In-beam γ-ray spectroscopy of Te 136 at relativistic energies

The reduced transition probability B(E2;01+→21+) to the first excited 2+ state of the neutron-rich nucleus Te136, with two protons and two neutrons outside the doubly magic Sn132 core, was measured via Coulomb excitation at relativistic energies at the RIKEN Radioactive Isotope Beam Factory. A value of B(E2)=0.191(26) e2b2 was extracted from the measured inelastic scattering cross section on an Au target taking into account the contributions from both Coulomb and nuclear excitations. In addition, an upper limit for the transition strength to a 2+ state of mixed-symmetry character in the excitation energy range of 1.5-2.2 MeV was determined and compared to the predictions of various theoretical calculations. Because of the high statistics gathered in the present experiment the error of the deduced B(E2) value is dominated by the systematic uncertainties involved in the analysis of Coulomb excitation experiments at beam energies around 150 MeV/u. Therefore, the latter are for the first time assessed in detail in the present work

Resonant soft X-ray scattering for polymer materials

Resonant Soft X-ray Scattering (RSoXS) was developed over the last a few years, and the first dedicated resonant soft X-ray scattering beamline for soft materials was constructed at the Advanced Light Source, LBNL. RSoXS combines soft X-ray spectroscopy with X-ray scattering and thus offers statistical information for 3D chemical morphology over a large length scale range from nanometers to micrometers. Using RSoXS to characterize multi-length scale soft materials with heterogeneous chemical structures, we have demonstrated that soft X-ray scattering is a unique complementary technique to conventional hard X-ray and neutron scattering. Its unique chemical sensitivity, large accessible size scale, molecular bond orientation sensitivity with polarized X-rays, and high coherence have shown great potential for chemically specific structural characterization for many classes of materials

Combining theory and experiment for X-ray absorption spectroscopy and resonant X-ray scattering characterization of polymers

An improved understanding of fundamental chemistry, electronic structure, morphology, and dynamics in polymers and soft materials requires advanced characterization techniques that are amenable to in situ and operando studies. Soft X-ray methods are especially useful in their ability to non-destructively provide information on specific materials or chemical moieties. Analysis of these experiments, which can be very dependent on X-ray energy and polarization, can quickly become complex. Complementary modeling and predictive capabilities are required to properly probe these critical features. Here, we present relevant background on this emerging suite of techniques. We focus on how the combination of theory and experiment has been applied and can be further developed to drive our understanding of how these methods probe relevant chemistry, structure, and dynamics in soft materials