Unveiling the multiscale morphology of chemically stabilized proton exchange membranes for fuel cells by means of Fourier and real space studies.

We recently presented the elaboration and functional properties of a new generation of hybrid membranes for PEMFC applications showing promising performances and durability. The strategy was to form, inside a commercial sPEEK membrane, via in situ sol-gel (SG) synthesis, a reactive SG phase able to reduce oxidative species generated during FC operation. In order to understand structure-properties interplay, we use a combination of direct space (AFM/3D FIB-SEM) and reciprocal space (SANS/WAXS) techniques to cover dimensional scales ranging from a hundred to few nanometers. AFM modulus images showed the SG phase distributed into spherical domains whose size increases with the SG uptake (ca. 100-200 nm range). Using contrast variation SANS, we observed that the sPEEK nanostructure is mostly unaffected by the insertion of the SG phase which presents a fractal-like multiscale structure. Additionally, the size of both the particles (aggregates/primary) is much too large to be sequestered in the ionic pathways of sPEEK. These findings indicate that the SG-NPs mainly grow within the amorphous interbundle domains. Noticeable rightward shift and widening of the ionomer peak are observed with the SG content, suggesting ion channel compression and greater heterogeneity of the ionic domain size. The SG phase develops in the interbundle regions with a limited impact on the water uptake but leading to a discontinuity of ionic conductivity. This Fourier and real spaces study clarifies the structure of the hybrid membranes and brings into the question the ideal distribution/localization of the SG phase to optimize the membrane's stabilization.

Organic Liquid Crystals as Single-Ion Li+ Conductors.

The development of new materials for tomorrow's electrochemical energy storage technologies, based on thoroughly designed molecular architectures is at the forefront of materials research. In this line, we report herein the development of a new class of organic lithium-ion battery electrolytes, thermotropic liquid crystalline single-ion conductors, for which the single-ion charge transport is decoupled from the molecular dynamics (i. e., obeys Arrhenius-type conductivity) just like in inorganic (single-)ion conductors. Focusing on an in-depth understanding of the structure-to-transport interplay and the demonstration of the proof-of-concept, we provide also strategies for their further development, as illustrated by the introduction of additional ionic groups to increase the charge carrier density, which results in a substantially enhanced ionic conductivity especially at lower temperatures.

The kinetics of water sorption in Nafion membranes: a small-angle neutron scattering study.

The optimization of the water management in proton exchange membrane fuel cells is a major issue for the large-scale development of this technology. In addition to the operating conditions, the membrane water sorption and transport processes obviously control the water management. The main objective of this work is to provide new experimental evidence based on the use of the small-angle neutron scattering (SANS) technique in order to allow a better understanding of water sorption processes. SANS spectra were recorded for membranes equilibrated with either water vapor or liquid. Sorption kinetics data were determined and the SANS spectra were analyzed using the method developed for extracting water concentration profiles across the membrane in operating fuel cells. The water concentration profiles across the membrane are completely flat, which indicates that the water diffusion within the membrane is not the limiting process. This result provides new insight into the numerous data published on these properties. For the first time, the swelling kinetics of a Nafion membrane immersed in liquid water is studied and a complete swelling is obtained in less than 1 min.

NMR and pulsed field gradient NMR approach of water sorption properties in Nafion at low temperature.

The water uptake and the water self-diffusion coefficient were measured in Nafion membranes at subzero temperatures. NMR spectroscopy was used to precisely quantify the actual concentration of water in membranes as a function of the temperature and their hydration rates at room temperature. We find that below 273 K the water concentration decreases with temperature to reach, at around 220 K, a limit value independent of the initial concentration. This regime is observed if the concentration at room temperature is higher than 10%. Below this concentration no membrane deswelling was observed. The water self-diffusion coefficient, measured by pulsed field gradient NMR in function of the temperature, is determined by the actual concentration C(T) whatever the concentration at room temperature. The concentration variation is attributed to a decrease in the relative humidity RH(T) of the water vapor surrounding the membrane induced by the simultaneous presence of supercooled water inside the membrane and ice outside the membrane.

Shear-induced isotropic to nematic transition of liquid-crystal polymers: identification of gap thickness and slipping effects.

The shear-induced isotropic-nematic transition is a generic property of liquid-crystalline polymer melts which is identified by the emergence in the isotropic phase of a strong birefringence above a critical shear rate. Although spectacular, this transition cannot be explained on the basis of a conventional approach (coupling with pretransitional fluctuations or with viscoelastic relaxation times). We investigate the asymptotic rheo-optical behavior of the shear-induced phase. The sample is an unentangled cyanobiphenyl side-chain polyacrylate. We show that the birefringence increases almost linearly and then saturates above a given shear rate depending on the gap thickness. Similarly, the shear stress versus shear rate curve exhibits for the same thickness and using the same substrate (quartz), an overshoot occurring at about the same shear rates followed by the stress plateau (indicating a stress-optical equivalence). In contrast, when the substrate is different, the stress-optical equivalence is no more valid. We interpret the overshoot and the plateau observed in birefringence and in shear stress curves as the entrance in a so far unidentified macroscopic sliding regime. The slipping mechanism is corroborated by the recent identification of macroscopic long-range correlations in unentangled polymer melt and contrasts with a description in terms of a nucleation-growth process as in wormlike micellar solutions.

New light on old wisdoms on molten polymers: conformation, slippage and shear banding in sheared entangled and unentangled melts.

The flow of viscoelastic materials is usually interpreted as resulting from intramolecular properties. Typically, the non-linear flow behaviour and sluggish relaxation dynamics in entangled polymers are interpreted by a disentanglement process. This molecular interpretation has never been validated by direct observation. We report here on in situ observations of polymer melts under steady-state shear flow using neutron scattering and particle tracking velocimetry. It is shown that the chains remain largely undeformed under steady-state shear flow whereas wall slippage and shear-banding are identified in both entangled and unentangled polymer melts. These observations are of prime importance; they reveal that the flow mechanism and its viscoelastic signature reflect a collective effect and not properties of individual chains.