Dynamic range of nanotube- and nanowire-based electromechanical systems

Nanomechanical resonators with high aspect ratio, such as nanotubes and nanowires are of interest due to their expected high sensitivity. However, a strongly nonlinear response combined with a high thermomechanical noise level limits the useful linear dynamic range of this type of device. We derive the equations governing this behavior and find a strong dependence [[proportional]dsqrt((d/L)[sup 5])] of the dynamic range on aspect ratio

Effects of sublattice symmetry and frustration on ionic transport in garnet solid electrolytes

We use rigorous group-theoretic techniques and molecular dynamics to investigate the connection between structural symmetry and ionic conductivity in the garnet family of solid Li-ion electrolytes. We identify new ordered phases and order-disorder phase transitions that are relevant for conductivity optimization. Ionic transport in this materials family is controlled by the frustration of the Li sublattice caused by incommensurability with the host structure at non-integer Li concentrations, while ordered phases explain regions of sharply lower conductivity. Disorder is therefore predicted to be optimal for ionic transport in this and other conductor families with strong Li interaction.Comment: 6 pages, 4 figures, and supplementary informatio

Basins of attraction of a nonlinear nanomechanical resonator

We present an experiment that systematically probes the basins of attraction of two fixed points of a nonlinear nanomechanical resonator and maps them out with high resolution. We observe a separatrix which progressively alters shape for varying drive strength and changes the relative areas of the two basins of attraction. The observed separatrix is blurred due to ambient fluctuations, including residual noise in the drive system, which cause uncertainty in the preparation of an initial state close to the separatrix. We find a good agreement between the experimentally mapped and theoretically calculated basins of attraction

Electronic, vibrational and transport properties of pnictogen substituted ternary skutterudites

First principles calculations are used to investigate electronic band structure and vibrational spectra of pnictogen substituted ternary skutterudites. We compare the results with the prototypical binary composition CoSb$_3$ to identify the effects of substitutions on the Sb site, and evaluate the potential of ternary skutterudites for thermoelectric applications. Electronic transport coefficients are computed within the Boltzmann transport formalism assuming a constant relaxation time, using a new methodology based on maximally localized Wannier function interpolation. Our results point to a large sensitivity of the electronic transport coefficients to carrier concentration and to scattering mechanisms associated with the enhanced polarity. The ionic character of the bonds is used to explain the detrimental effect on the thermoelectric properties

Factors affecting cyclic durability of all-solid-state lithium batteries using poly(ethylene oxide)-based polymer electrolytes and recommendations to achieve improved performance

A detailed experimental analysis of the factors affecting cyclic durability of all-solid-state lithium batteries using poly(ethylene oxide)-based polymer electrolytes was published in EES by Nakayama et al. We use quantum mechanics to interpret these results, identifying processes involved in the degradation of rechargeable lithium batteries based on polyethylene oxide (PEO) polymer electrolyte with LiTFSI. We consider that ionization of the electrolyte near the cathode at the end of the recharge step is probably responsible for this degradation. We find that an electron is likely removed from PEO next to a TFSI anion, triggering a sequence of steps leading to neutralization of a TFSI anion and anchoring of another TFSI to the PEO. This decreases the polymer conductivity near the cathode, making it easier to ionize additional PEO and leading to complete degradation of the battery. We refer to this as the Cathode Overpotential Driven Ionization of the Solvent (CODIS) model. We suggest possible ways to confirm experimentally our interpretation and propose modifications to suppress or reduce electrolyte degradation

Correlated electron states and transport in triangular arrays

We study correlated electron states in frustrated geometry of a triangular lattice. The interplay of long range interactions and finite residual entropy of a classical system gives rise to unusual effects in equilibrium ordering as well as in transport. A novel correlated fluid phase is identified in a wide range of densities and temperatures above freezing into commensurate solid phases. The charge dynamics in the correlated phase is described in terms of a height field, its fluctuations, and topological defects. We demonstrate that the height field fluctuations give rise to a ``free'' charge flow and finite dc conductivity. We show that freezing into the solid phase, controlled by the long range interactions, manifests itself in singularities of transport properties.Comment: 19 pages, 10 figure

Capacitive Spring Softening in Single-Walled Carbon Nanotube Nanoelectromechanical Resonators

We report the capacitive spring softening effect observed in single-walled carbon nanotube (SWNT) nanoelectromechanical (NEM) resonators. The nanotube resonators adopt dual-gate configuration with both bottom-gate and side-gate capable of tuning the resonance frequency through capacitive coupling. Interestingly, downward resonance frequency shifting is observed with increasing side-gate voltage, which can be attributed to the capacitive softening of spring constant. Furthermore, in-plane vibrational modes exhibit much stronger spring softening effect than out-of-plan modes. Our dual-gate design should enable the differentiation between these two types of vibrational modes, and open up new possibility for nonlinear operation of nanotube resonators.Comment: 12 pages/ 3 figure

Atomistic Description of Ionic Diffusion in PEO-LiTFSI: Effect of Temperature, Molecular Weight, and Ionic Concentration

Understanding the ionic diffusion mechanism in polymer electrolytes is critical to the development of advanced lithium-ion batteries. We report here molecular dynamics-based characterization of structures and diffusion in poly(ethylene oxide) (PEO) with lithium and bis(trifluoromethysulfonyl)imide (TFSI) ions imbedded into the PEO structure. We consider a range of temperatures (360–480 K), molecular weights (43, 22, 10, and 2 chains with 23, 45, 100, and 450 EO monomers, respectively), and ion concentrations (r = 0.02, 0.04, 0.06, and 0.08 Li:EO) for which there is experimental data. The found dependence of the diffusion coefficients on these variables is in good agreement with experimental measurements. We then analyze how the diffusion performance depends on details of the atomistic diffusion mechanism, the motion of the Li and TFSI along the polymer chains and hopping between them, the role of polymer motion, the temperature dependence of the intrachain and interchain diffusion contributions to the total ionic diffusion coefficients, and how these depend on ionic concentration and molecular weight. The most diffusive Li atoms exhibit frequent interchain hopping, whereas the least diffusive Li atoms oscillate or “shift” between two or more polymer chains. These shifts may affect the segmental motion of the PEO–LiTFSI polymer that is expected to be important for fast lithium-ion diffusion. The excellent agreement between experiment and theory validates the approach and methodology used in this study, setting the stage for applying this methodology to predicting how to modify the polymer structure to increase ionic conductivity for a new generation of electrochemical materials