Examination of the fundamental relation between ionic transport and segmental relaxation in polymer electrolytes
Not Available
Wang, Yangyang (ORCID:0000000170429804)↗
Engineering topics
Agapov, Alexander L
Publications and source records attributed to Agapov, Alexander L.
Macroscopic Properties of Restacked, Redox-Liquid Exfoliated Graphite and Graphite Mimics Produced in Bulk Quantities
The excellent properties exhibited by monolayer graphene have spurred the development of exfoliation techniques using bulk graphite to produce large quantities of pristine monolayer sheets. Development of simple chemistry to exfoliate and intercalate graphite and graphite mimics in large quantities is required for numerous applications. To determine the macroscopic behavior of restacked, exfoliated bulk materials, a systematic approach is presented using a simple, redox-liquid sonication process along to obtain large quantities of 2D and 3D hexagonally layered graphite, molybdenum disulfi de, and boron nitride, which are subsequently characterized to observe chemical and structural changes. For MoS 2 sonicated with the antioxidant sodium bisulfi te, results from Raman spectroscopy, X-ray diffraction, and electron microscopy indicate the presence of distorted phases from different polymorphs, and apparent nanotube structures in the bulk, restacked powder. Furthermore, using thermograviemtric analysis, the antioxidant enhances the resistance to oxidative degradation of MoS 2 , upon thermal treatment up to 900 C. The addition of the ionic antioxidant decreased dispersion stability in non-polar solvent, suggesting decreased compatibility with non-polar systems. Using simple chemical methods, the ability to generate tailored multidimensional layered materials with unique macroscopic properties is critical for numerous applications, including electrical devices, reinforced polymer composites, lithium ion capacitors, and chemical sensing.
Srivastava, Vikram K↗
Room temperature reduction of multilayer graphene oxide film on a copper substrate: Penetration and participation of coper phase in redox reactions.
A self-reduction of graphene oxide (GO) at room temperature after prolonged storage on a copper substrate is evidenced by decrease of oxygen content and a dramatic, 6 orders in magnitude, increase in dc conductivity. Experiments revealed that the stored GO film contains copper hydroxide phase embedded in the reduced GO structure.
Voylov, Dmitry N↗
High Yield Synthesis of Mesoscopic Conductive and Dispersible Carbon Nanostructures via Ultrasonication of Commercial Precursors
The need to produce large quantities of graphenic materials displaying excellent conductivity, thermal resistance, and tunable properties for industrial applications has spurred interest in new techniques for exfoliating graphite. In this paper, sonication-assisted exfoliation of graphitic precursors in the presence of chloroform is shown to produce chemically and structurally unique exfoliated graphitic materials in high yields. These exfoliated graphites, referred to as mesographite and mesographene, respectively, exhibit unique properties which depend on the number of layers and exfoliation conditions. Structural characterization of mesographene reveals the presence of nanoscale two-dimensional graphene layers, and threedimensional carbon nanostructures sandwiched between layers, similar to those found in ball-milled and intercalated graphites. The conductivities of mesographite and mesographene are 2700 and 2000 S/m, respectively, indicating high conductivity despite flake damage. Optical absorption measurements of mesographite sonicated in various solvents showed significant changes in dispersion characteristics, and also indicated significant changes to mesoscopic colloidal behavior. A mechanism for functionalization and formation of capped carbon nanostructures is proposed by integrating the chemical and structural characterization in relation to the various carbon structures observed by electron microscopy. Composites based on common polymers were prepared by solution processing, and changes in thermal properties indicate improved dispersion of mesographite in polar polymers.
Srivastava, Vikram K↗
Dynamics at the Polymer/Nanoparticle Interface in Poly(2-vinylpyridine)/Silica Nanocomposites.
The static and dynamic properties of poly(2-vinylpyridine)/silica nanocomposites are investigated by temperature modulated differential scanning calorimetry, broadband dielectric spectroscopy (BDS), small-angle X-ray scattering (SAXS), and transmission electron microscopy. Both BDS and SAXS detect the existence of an interfacial polymer layer on the surface of nanoparticles. The results show that whereas the calorimetric glass transition temperature varies only weakly with nanoparticle loading, the segmental mobility of the polymer interfacial layer is slower than the bulk polymer by 2 orders of magnitude. Detailed analysis of BDS and SAXS data reveal that the interfacial layer has a thickness of 4 6 nm irrespective of the nanoparticle concentration. These results demonstrate that in contrast to some recent articles on polymer nanocomposites, the interfacial polymer layer is by no means a dead layer . However, its existence might provide some explanation for controversies surrounding the dynamics of polymer nanocomposites.
Holt, Adam P↗
Carbon nanomaterial produced by microwave exfoliation of graphite oxide: new insights.
We present detailed characterization of graphene-like material obtained through microwave stimulated exfoliation of graphite oxide (GO). Properties of this material were studied by multiple techniques including, among others, X-ray photoelectron spectroscopy, mass-spectroscopy, infrared and Raman spectroscopy, scanning electron microscopy and broadband dielectric spectroscopy. Specific surface area and volume of microwave exfoliated graphite oxide reached 600 m2 g1 and 6 cm3 g1, respectively. It is shown that during such an explosive reduction process the sample emits CO2, CO and H2O and, in some cases, SO2 gases. The resulting reduced material exhibits IR spectra similar to that of graphite and a dc-conductivity of 0.12 S cm1.
Shulga, Y. M.↗
Chain and Segmental Dynamics of Poly(2-vinlylpyridine)
The influence of different oxide nanoparticles on segmental and chain dynamics of poly(2-vinylpyridine) is investigated by broadband dielectric spectroscopy (BDS), dynamic mechanical measurements, and calorimetry. While significant changes in rheological properties are observed with increasing nanoparticle loading, only weak effects are found in the glass transition temperature, the segmental mobility, and fragility. These results are discussed in the context of recent controversies in studies of polymer nanocomposites and polymer thin films.
Holt, Adam P↗
Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes
Not Available
Wang, Yangyang↗
Effect of polymer-nanoparticle interactions on the glass transition dynamics and the conductivity mechanism in polyurethane titanium dioxide nanocomposites
We report on the glass transition dynamics and the conductivity properties of a nanodielectric system composed of pre-synthesized TiO{sub 2} nanoparticles embedded in thermoplastic polyurethane. Increase of TiO{sub 2} loading results in enhanced segmental mobility of the composites and less steep temperature dependence, i.e., lower fragility index. The decrease in the fragility index and glass transition temperature is discussed based on the FTIR results. We observe different behavior of conductivity for temperatures above and below the glass transition temperature. At high temperatures the composites exhibit conductivity values more than 2 orders of magnitude higher than those in the pristine matrix. At the same time, at sub-Tg temperatures composites are characterized by superior electrical insulation properties compared to pristine matrix material. Such drastic temperature dependence of the conductivity/insulating ability of the flexible and light-weight, low-Tg composite material can be utilized in various applications including sensing and temperature switching materials.
36 MATERIALS SCIENCE↗
Effect of PolarInteractions on Polymer Dynamics
Despite significant experimental and theoretical efforts, a fundamental understanding of how the chemical structure influences various dynamic processes in glass-forming materials and polymers remains a topic of active discussion. The present study analyzes the influence of polar interactions on the temperature dependences of segmental and chain dynamics in polymers. We found that segmental dynamics slow down (the glass transition temperature Tg increases) and have steeper temperature dependence (higher fragility index m) when a polar group is attached directly to the polymer backbone. However, when a polar group is separated from the backbone by a side group, both Tg and m become complex functions of the monomer s polarity and the relative position of the polar group. Our analysis revealed unexpected effect of polar interactions on chain dynamics: chain modes in polar polymers are coupled to the segmental dynamics stronger than in nonpolar polymers with similar fragilities. This results in a steeper temperature dependence of chain dynamics in polar polymers. How the polar interactions affect the coupling of chain and segmental modes remains unclear.
Agapov, Alexander L↗
An assessment of comparaqtive methods for approaching electrode polarization in dielectric permittivity measurements
We examine the validity of three common methods for analysis and correction of the electrode polarization (EP) effect in dielectric spectroscopy measurements of conductive liquid samples. The methods considered are (i) algorithmic treatment by modeling the EP behavior at constant phase angle, (ii) varying the size of the electrode gap, and (iii) polypyrrole (PPyPss) layered electrodes. The latter is a relatively recent innovation suggested to be an efficient solution. We demonstrate that PPyPss coated electrodes do not diminish the effect of EP, and even add relaxation processes of its own. Our conclusion is that these polymer coated electrodes are not suitable for the correction of electrode polarization.
Ben Ishai, Paul↗
Translation-rotation decoupling and nonexponentiality in room temperature ionic liquids
Using a combination of light scattering techniques and broadband dielectric spectroscopy, we have measured the temperature dependence of structural relaxation time and self diffusion in three imidazolium-based room temperature ionic liquids: [bmim][NTf2], [bmim][PF6], and [bmim][TFA]. A detailed analysis of the results demonstrates that self diffusion decouples from structural relaxation in these systems as the temperature is decreased toward Tg. The degree to which the dynamics are decoupled, however, is shown to be surprisingly weak when compared to other supercooled liquids of similar fragility. In addition to the weak decoupling, we demonstrate that the temperature dependence of the structural relaxation time in all three liquids can be well described by a single Vogel-Fulcher-Tamann function over 13 decades in time from 10 11 s up to 102 s. Furthermore, the stretching of the structural relaxation is shown to be temperature independent over the same range of time scales, i.e., time temperature superposition is valid for these ionic liquids from far above the melting point down to the glass transition temperature.We suggest that these phenomena are interconnected and all result from the same underlying mechanism strong and directional intermolecular interactions.
Griffin, Phillip↗
Decoupling charge transport from the structural dynamics in room temperature ionic liquids
Light scattering and dielectric spectroscopy measurements were performed on the room temperature ionic liquid (RTIL) [C4mim][NTf2] in a broad temperature and frequency range. Ionic conductivity was used to estimate self-diffusion of ions, while light scattering was used to study structural relaxation. We demonstrate that the ionic diffusion decouples from the structural relaxation processes the temperature of the sample decreases toward Tg. The strength of the decoupling appears to be significantly lower than that expected for a supercooled liquid of similar fragility. The structural relaxation process in the RTIL follows well the high-temperature mode coupling theory (MCT) scenario.Using the MCT analysis we estimated the dynamic crossover temperature in [C4mim][NTf2]to be Tc ~ 225 ± 5 K. However, our analysis reveals no sign of the dynamic crossover in the ionic diffusion process.
36 MATERIALS SCIENCE↗
Prolonged Blinking with TERS Probes
Tip-enhanced Raman spectroscopy (TERS), an emerging technique combining scanning probe microscopy (SPM) and Raman spectroscopy, provides the sensitivity and selectivity necessary for chemical imaging with nanoscale resolution. We demonstrate that coating the fragile plasmonic structures used to enhance the electric field with a protective layer improves significantly its mechanical, chemical, and thermal stability without loss of the extreme optical enhancement that appears as a blinking phenomenon. This observation provides important information on the mechanism of blinking. The fact that TERS blinking from a polymer layer is preserved when the analyte is separated from the plasmonic nanostructure by a 3 nm thick coating proves that chemical enhancement and charge transfer do not play a significant role in the blinking. Rather, thermally activated diffusion appears to be the dominant mechanism. While extreme enhancement persists only for minutes for an unprotected silver-coated tip, it persists for tens of hours with plasmonic structures coated by an ultrathin layer of alumina (Al2O3), opening broader opportunities for the study of blinking and for chemical imaging and sensing based on plasmonic structures.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Decoupling Ionic Conductivity from Structural Relaxation: A Way to Solid Polymer Electrolytes?
Using broadband dielectric spectroscopy, we studied the temperature dependence of ionic conductivity and structural relaxation in a number of polymers. We demonstrate that temperature dependence of ionic conductivity can be decoupled from structural relaxation in a material specific way. We show that the strength of the decoupling correlates with the steepness of the temperature dependence of structural relaxation in the polymer, i.e., with its fragility. We ascribe the observed result to stronger frustration in chain packing characteristic for more fragile polymers. We speculate that employment of more fragile polymers might lead to design of polymers with higher ionic conductivity.
36 MATERIALS SCIENCE↗