Polymer electrolyte membranes comprising poly(vinylidene fluoride)−hexafluoropropene (PVdF−HFP) copolymer plasticized with a solution of LiSO3CF3, LiN(SO2CF3)2, or LiPF6 in oligomeric poly(ethylene glycol) dimethyl ethers (PEGDME, M w = 250, 400, and 500) were prepared by hot-melt-rolling or solvent-casting techniques. Since the electrolytes containing PEGDME400 and PEGDME500 are “dry” with essentially no volatile components up to 150 °C, we have dubbed them PEO-like. Their thermal stability, mechanical strength, conductivity, electrochemical stability window, and Li/electrolyte interface stability were characterized. Plasticizing PVdF−HFP with the PEGDME/LiX solutions disordered the polymer structure leading to polymer electrolytes having lower crystallinity than the polymer host itself. The mechanical strength of the electrolyte membranes varied depending on the PVdF content. Tensile strength (stress) as high as 420 psi at an elongation-at-break value (strain) of 75% was observed. The conductivities of the electrolytes correlated with the molecular weights of PEGDME as well as the concentration of the Li salt, and most of the electrolytes prepared showed room-temperature conductivities of greater than 10-4 S/cm. The high room-temperature conductivity of these electrolytes compared to PEO-based electrolytes is attributed to the high mobility of the ionic charge carriers. The Li/electrolyte interface stability under open-circuit conditions was found to be good as assessed from the small change in the interfacial impedance for the measured case of the PVdF−PEGDME500−LiN(SO2CF3)2 electrolyte. This electrolyte also showed oxidation stability up to 4.5V versus Li+/Li on Al, Ni, and stainless steel (SS) and reduction stability down to 0.0V versus Li+/Li on both Ni and SS. The applicability of these electrolytes in batteries was demonstrated by the fabrication and testing of Li/oxygen and Li/LiMn2O4 cells.
Polymer nanocomposites (PNCs) are important materials that are widely used in many current technologies and potentially have broader applications in the future due to their excellent property tunability, light weight, and low cost. However, expanding the limits in property enhancement remains a fundamental scientific challenge. Here, we demonstrate that well-dispersed, small (diameter ∼1.8 nm) nanoparticles with attractive interactions lead to unexpectedly large and qualitatively different changes in PNC structural dynamics in comparison to conventional nanocomposites based on particles of diameters ∼10-50 nm. At the same time, the zero-shear viscosity at high temperatures remains comparable to that of the neat polymer, thereby retaining good processability and resolving a major challenge in PNC applications. Our results suggest that the nanoparticle mobility and relatively short lifetimes of nanoparticle-polymer associations open qualitatively different horizons in the tunability of macroscopic properties in nanocomposites with a high potential for the development of advanced functional materials.
In recent years it has become clear that the interfacial layer formed around nanoparticles in polymer nanocomposites (PNCs) is critical for controlling their macroscopic properties. The interfacial layer occupies a significant volume fraction of the polymer matrix in PNCs and creates strong intrinsic heterogeneity in their structure and dynamics. Here, we focus on analysis of the structure and dynamics of the interfacial region in model PNCs with well-dispersed, spherical nanoparticles with attractive interactions. First, we discuss several experimental techniques that provide structural and dynamic information on the interfacial region in PNCs. Then, we discuss the role of various microscopic parameters in controlling structure and dynamics of the interfacial layer. The analysis presented emphasizes the importance of the polymer-nanoparticle interactions for the slowing down dynamics in the interfacial region, while the thickness of the interfacial layer appears to be dependent on chain rigidity, and has been shown to increase with cooling upon approaching the glass transition. Aside from chain rigidity and polymer-nanoparticle interactions, the interfacial layer properties are also affected by the molecular weight of the polymer and the size of the nanoparticles. In the final part of this focus article, we emphasize the important challenges in the field of polymer nanocomposites and a potential analogy with the behavior observed in thin films.
The addition of nanoparticles to a polymer matrix is a well-known process to improve the mechanical properties of polymers. Many studies of mechanical reinforcement in polymer nanocomposites (PNCs) focus on rubbery matrices; however, much less effort concentrates on the factors controlling the mechanical performance of the technologically important glassy PNCs. This paper presents a study of the effect of the polymer molecular weight (MW) on the overall mechanical properties of glassy PNCs with attractive interaction by using Brillouin light scattering. We found that the mechanical moduli (bulk and shear) have a nonmonotonic dependence on MW that cannot be predicted by simple rule of mixtures. The moduli increase with increasing MW up to 100 kg/mol followed by a drop at higher MW. We demonstrate that the change in the mechanical properties of PNCs can be associated with the properties of the interfacial polymer layer. The latter depend on the interfacial chain packing and stretching, as well as polymer bridging, which vary differently with the MW of the polymer. These competing contributions lead to the observed nonmonotonic variations of the glassy PNC moduli with MW. Our work provides a simple, cost-effective, and efficient way to control the mechanical properties of glassy PNCs by tuning the polymer chain length. Our finding can be beneficial for the rational design of PNCs with desired mechanical performance.
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