An “interaction-mediating” strategy towards enhanced solubility and redox properties of organics for aqueous flow batteries

Aqueous redox flow batteries using electroactive organic materials are currently attracting significant attention. However, the influence of supporting electrolytes on the aqueous solubility, electrochemical reversibility and chemical stability of the organic components has rarely been investigated. Here, a new electrolyte design strategy towards enhanced solubility and chemical stability of active materials is proposed by using interaction-mediating species. 3 molality aqueous imidazolium chlorides, with high ionic conductivity and water-like flowability, enable a record aqueous solubility of 4.3 M for a commercially available nitroxyl radical and reversible 2e^{-} reaction of unmodified methyl viologen at moderate concentrations. With 0.6 M electrolyte, flow cell shows remarkable chemical stability of the nitroxyl radical, excellent cycling stability over 250 cycles at 80 mA cm^{-2}, and a peak power density of 121.6 mW cm^{-2} at 175 mA cm^{-2}. Furthermore, nitroxyl radical catholyte with a concentration of 3 M is tested in a flow cell. It maintains an impressive steady energy efficiency of 65% at 30 mA cm^{-2}. This work paves a new way for the development of high performance aqueous electrolytes based on organic materials

Dynamics, cation conformation and rotamers in guanidinium ionic liquids with ether groups

Ionic liquids are modern materials with a broad range of applications, including electrochemical devices, the exploitation of sustainable resources and chemical processing. Expanding the chemical space to include novel ion classes allows for the elucidation of novel structure-property relationships and fine tuning for specific applications. We prepared a set of ionic liquids based on the sparsely investigated pentamethyl guanidinium cation with a 2-ethoxy-ethyl side chain in combination with a series of frequently used anions. The resulting properties are compared to a cation with a pentyl side chain lacking ether functionalization. We measured the thermal transitions and transport properties to estimate the performance and trends of this cation class. The samples with imide-type anions form liquids at ambient temperature, and show good transport properties, comparable to imidazolium or ammonium ionic liquids. Despite the dynamics being significantly accelerated, ether functionalization of the cation favors the formation of crystalline solids. Single crystal structure analysis, ab initio calculations and variable temperature nuclear magnetic resonance measurements (VT-NMR) revealed that cation conformations for the ether- and alkyl-chain-substituted are different in both the solid and liquid states. While ether containing cations adopt compact, curled structures, those with pentyl side chains are linear. The Eyring plot revealed that the curled conformation is accompanied by a higher activation energy for rotation around the carbon-nitrogen bonds, due to the coordination of the ether chain as observed by VT-NMR

Plasmon-Coupled Gold Nanoparticles in Stretched Shape-Memory Polymers for Mechanical/Thermal Sensing

The organization of plasmonic nanoparticles (NPs) determines the strength and polarization dependence of coupling of their surface plasmons. In this study, plasmon coupling of spherical Au NPs with an average diameter of 15 nm was investigated in shape-memory polymer films before and after mechanical stretching and then after thermally driving shape recovery. Clusters of Au NPs form when preparing the films that exhibit strong plasmon coupling. During stretching, a significant polarization-dependent response develops, where the optical extinction maximum corresponding to the surface plasmon resonance is redshifted by 19 nm and blueshifted by 7 nm for polarization parallel and perpendicular to the stretching direction, respectively. This result can be explained by non-uniform stretching on the nanoscale, where plasmon coupling increases parallel to the shear direction as Au NPs are pulled into each other during stretching. The polarization dependence vanishes after shape recovery, and structural characterization confirms the return of isotropy consistent with complete nanoscale recovery of the initial arrangement of Au NPs. Simulations of the polarized optical responses of Au NP dimers at different interparticle spacings establish a plasmon ruler for estimating the average interparticle spacings within the experimental samples. An investigation of the temperature-dependent recovery behavior demonstrates an application of these materials as optical thermal history sensors

Changes in the bending modulus of AOT based microemulsions induced by the incorporation of polymers in the water core

The bending modulus k is known to be a crucial parameter for the stability of the droplet phase in microemulsion systems. For AOT based water in oil microemulsions the bending modulus of the surfactant has values close to kBT but can be influenced by the presence of polymers. In this work we focus on the water soluble polymer polyethylene glycol and how it influences the bending modulus. An increase by a factor of three is found. For the correct evaluation of the bending modulus via percolation temperatures and droplet radii, thus by dielectric spectroscopy and small angle X-ray scattering, the determination of the radii right at the percolation temperature is crucial as we will show, although it is often neglected. In order to precisely determine the droplet radii we will present a global fitting model which provides reliable results with a minimum number of free fitting parameters

Polymer loaded microemulsions: Changeover from finite size effects to interfacial interactions

Form fluctuations of microemulsion droplets are observed in experiments using dielectric spectroscopy (DS) and neutron spin echo spectroscopy (NSE). Previous work on dioctyl sodium sulfosuccinate based water in oil microemulsions in the droplet phase has shown that adding a water soluble polymer (Polyethylene glycol M = 1500 g mol−1) modifies these fluctuations. While for small droplet sizes (water core radius rc < 37 Å) compared to the size of the polymer both methods consistently showed a reduction in the bending modulus of the surfactant shell as a result of polymer addition, dielectric spectroscopy suggests the opposite behaviour for large droplets. This observation is now confirmed by NSE experiments on large droplets. Structural changes due to polymer addition are qualitatively independent of droplet size. Dynamical properties, however, display a clear variation with the number of polymer chains per droplet, leading to the observed changes in the bending modulus. Furthermore, the contribution of structural and dynamical properties on the changes in bending modulus shifts in weight. With increasing droplet size, we initially find dominating finite size effects and a changeover to a system, where interactions between the confined polymer and the surfactant shell dominate the bending modulus.I. INTRODUCTIO

Polymer conformation in nanoscopic soft confinement

We study the conformation of a polymer (polyethylene glycol) in a nanoscopic soft confinement with attractive walls. The polymer is added to a water-in-oil microemulsion based on the deuterated anionic surfactant AOT, d-octane and D2O. Three different droplet sizes and up to three polymers per droplet are investigated with small angle scattering combining X-rays and neutrons. This allows determining the confinement size and polymer conformation on identical samples. Whereas polymer conformation in bulk is found to be well described with the model of a Gaussian coil its radius of gyration is drastically increased in the droplet. At the same time it is compressed on a local scale. This supports the picture of a polymer strongly adsorbed on the surfactant layer with a thickness of several Angstroms

Multiple recrystallization behavior of poly(1,1-dimethysilacyclobutane): A combined calorimetric and small angle X-ray scattering study

The crystallization and melting behavior of a series of poly(1,1-dimethysilacyclobutane) (PDMSB) samples accessible via living anionic polymerization protocols with different molar masses were studied by differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS) and X-ray diffraction (XRD). It has been found that in the cooling process only one crystallization exotherm was observed by using DSC, but in subsequent heating two clear endotherms appeared. DSC measurements additionally revealed that there will be two melting peaks when the isothermal crystallization temperature, T-c, is low enough, but only one melting peak could be obtained when T-c is high. The value of the lower melting peak T-m1 increased with T-c, showing the increase of lamella thickness due to increase of T-c, which was also evidenced by using SAXS measurements. However, the value of the higher melting peak T-m2 stayed almost constant with T-c. XRD analysis showed that there is only one crystal form independent of T-c. While SAXS results revealed only one long range order, indicating this multiple endotherms phenomenon was caused by the recrystallization process during heating, but not isothermal thickening and thinning process as observed for e.g. poly(ethylene oxide)s (PEOs) with low molar masses. Heating rate dependent DSC experiments showed that there are two recrystallization processes with different time scales. The recrystallization at low temperature always showed up independent of heating rate while the recrystallization at high temperature showed up only when the heating rate was very low. This interesting phenomenon was explained by the different energy barrier for the recrystallization process at low and high temperature as shown by in situ SAXS measurements during heating. (C) 2013 Elsevier Ltd. All rights reserved