Robust and Wide Temperature-Range Zinc Metal Batteries with Unique Electrolyte and Substrate Design

Rechargeable zinc metal batteries are promising for large-scale energy storage. However, their practical application is limited by harsh issues such as uncontrollable dendrite growth, low Coulombic efficiency, and poor temperature tolerance. Herein, a unique design strategy using γ-valerolactone-based electrolyte and nanocarbon-coated aluminum substrate was reported to solve the above problems. The electrolyte with extremely low freezing point and high thermal stability enables the symmetric cells with long cycle life over a wide temperature range (−50 °C to 80 °C) due to its ability to regulate zinc nucleation and preferential epitaxial growth. Besides, the nanocarbon-coated aluminum substrate can also promote a higher Coulombic efficiency over a wide temperature range in contrast to the low Coulombic efficiency of copper substrates with significant irreversible alloying reactions because this unique substrate with excellent chemical stabilization can homogenize the interfacial electron/ion distribution. The optimized zinc metal capacitors can operate stably under various temperature conditions (2000 cycles at 30 °C with 66 % depth of discharge and 1200 cycles at 80 °C with 50 % depth of discharge). This unique electrolyte and substrate design strategy achieves a robust zinc metal battery over a wide temperature range.     

Analytical Modelling of Electron-coupled Ion Transfers with Immobilized vs Soluble Redox Transducer at Thick Film-modified Electrodes

Analytical theoretical solutions are deduced for the current-potential response, concentration profiles and interfacial potentials of electron-coupled ion transfers in the cyclic voltammetry with thick film-modified electrodes. The theory covers a wide variety of possible situations, namely, the redox transducer can be either immobilized on the working electrode or freely diffusing in the organic film, and the ion transfer can be either simple or complicated by homogeneous chemical processes. A comparative and comprehensive study of each case is performed, establishing the key parameters that define the behaviour of the system, as well as guidelines to analyse its electrochemical signal.     

Synthesis and evaluation of carboxymethyl chitosan for glycopeptide enrichment

Glycans are known to be involved in a variety of biological processes throughout human physiology. Mass spectrometry has demonstrated itself as powerful analytical tool for quantitative and structural characterization of glycans. Studying these molecules at the glycopeptide level however, offers distinct advantages, namely the ability to characterize both the glycan and peptide fragments simultaneously, and moreover the ability to assign site specific heterogeneity. In light of this, peptides often dominate the spectrum and hinder the ionization efficiency of glycopeptides. For this reason, enrichment protocols prior to downstream MS analysis need to be developed. Here, we discuss the synthesis and use of carboxymethyl chitosan (CMCH) to enrich glycopeptides from a 12 protein mixture for MS analysis. This protocol was compared to a commercially available glycopeptide enrichment kit offered by EMD Millipore through the use of tandem mass tags (TMT) for relative quantification. Using this approach, we identified 98 unique N-linked glycopeptides and observed, that CMCH was able to enrich more sialylation than the commercial kit. In addition, we observed a trend based on TMT reporter ratios with respect to increasing sialylation. This corroborated that this stationary phase was exhibiting a mixed-mode enrichment through both hydrophilic interaction liquid chromatography (HILIC) and weak anion exchange (WAX) principles.     

Ternary mutual diffusion coefficients of aqueous {l-dopa (1) + β-CD (2)} solutions at T = 298.15 K

Ternary mutual diffusion coefficients (D₁₁, D₂₂, D₁₂ and D₂₁) measured by the Taylor dispersion method are reported for aqueous solutions of {levodopa (l-dopa) + β-cyclodextrin (β-CD)} solutions at T = 298.15 K and concentrations up to 0.007 mol · dm⁻³. Significant effects on the diffusion were observed, suggesting interactions between this carbohydrate and l-dopa. Support for this came from ¹H NMR spectroscopy, which shows that these effects are due to formation of 1:1 (β-CD:l-dopa) complexes.     

Bound state solutions of D‐dimensional schrödinger equation with exponential‐type potentials

In this article, using an exactly‐solvable multiparameter exponential‐type potential we propose a unified treatment of the analytical bound—state solutions of the Schrödinger equation for exponential‐type potentials in D‐dimensions. Our proposal accepts different approximations to the centrifugal term; however, its usefulness is exemplified in the frame of the Green and Aldrich approach. This fact enables us to compare our results with specific potentials found in the literature and that are obtained here as particular cases of our proposal. That is, instead of solving a specific exponential‐type potential, by resorting each time to a specialized method, the energy spectra and wavefunctions are derived straightforward from the proposed approach. Furthermore, our proposal can be used as an alternative way in the search of solutions to new exponential‐type potentials besides that one can study different approximations to the term . © 2014 Wiley Periodicals, Inc.     

Ideal and non-ideal behaviour of {1-butyl-1-methylpyrrolydinium bis(trifluoromethylsulfonyl)imide + γ-butyrolactone} binary mixtures

Density, electrical conductivity and viscosity of binary liquid mixtures of 1-butyl-1-methylpyrrolydinium bis(trifluoromethylsulfonyl)imide, [bmpyrr][NTf₂], with γ-butyrolactone (GBL) were measured at temperatures from (293.15 to 323.15) K and at atmospheric pressure over the whole composition range. Excess molar volumes have been calculated from the experimental densities and fitted with the Redlich–Kister polynomial equation. These values are positive over the whole range of ionic liquid mole fraction and at all temperatures. In the range between 0.55 and 0.6 [bmpyrr][NTf₂] mole fraction, an ideal behaviour of the ionic liquid mixture with molecular solvent was observed for the first time. Other volumetric properties, such as isobaric thermal expansion coefficients, partial molar volumes and partial molar volumes at infinite dilution have been also calculated, in order to obtain information about interactions between GBL and selected ionic liquid. Positive values of these properties for both components also indicate weaker interactions between GBL and IL compared to the pure components. From the viscosity results, the Angell strength parameter was calculated and found to be 3.24 indicating that [bmpyrr][NTf₂] is a “fragile” liquid. From the volumetric and transport properties obtained, formation of the [bmpyrr]⁺ micellar structures was also discussed. All the results are compared to those obtained for imidazolium-based ionic liquid with GBL.     

Polymer contribution to the thermal conductivity and viscosity in a dilute solution (Fraenkel Dumbbell model)

The phase-space kinetic theory for polymeric liquid mixtures is used to obtain an expression for the polymer contribution to the thermal conductivity of a nonflowing, dilute solution of polymers, where the polymer molecules are modeled as Fraenkel dumbbells. This theory takes into account three mechanisms for the energy transport: diffusion of kinetic energy (including the Öttinger-Petrillo term), diffusion of intramolecular energy, and the work done against the intramolecular forces. This paper is an extension of previous developments for the Hookean dumbbell model and the finitely-extensible dumbbell model. A comparison among the dumbbell results suggests that the thermal conductivity increases with chain stiffness. In addition, the zero-shear-rate viscosity and first normal-stress coefficient are also given for the Fraenkel dumbbell model.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Experimental analysis of the steady-state behaviour of beam systems with discontinuous support

This paper deals with the experimental analysis of the long-term behaviour of periodically excited linear beams supported by a one-sided spring or an elastic stop. Numerical analysis of the beams showed subharmonic, quasi-periodic and chaotic behaviour. Furthermore, in the beam system with the one-sided spring three different routes leading to chaos were found. Because of the relative simplicity of the beam systems and the variety of calculated nonlinear phenomena, experimental setups are made of the beam systems to verify the numerical results. The experimental results correspond very well with the numerical results as far as the subharmonic behaviour is concerned. Measured chaotic behaviour is proved to be chaotic by calculating Lyapunov exponents of experimental data.

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Sommario Il presente lavoro concerne l'analisi sperimentale del comportamento a regime di travi lineari, su supporti elastici nonlineari discontinui, eccitate periodicamente. L'analisi numerica dei sistemi in esame ha evidenziato risposte subarmoniche, quasi-periodiche e caotiche, nonchè l'esistenza, nel caso di trave con una molla laterale, di tre differenti percorsi verso il caos. La relativa semplicità dei sistemi di travi ha consentito di procedere ad una verifica sperimentale dei risultati numerici e della varietà dei fenomeni nonlineari da essi evidenziati. La corrispondenza fra risultati sperimentali e numerici è molto buona nel caso di risposta subarmonica. Il comportamento caotico sperimentale è stato convalidato attraverso il calcolo degli esponenti di Lyapunov a partire dai relativi dati.

     

Nonlinear interactions and chaotic dynamics of suspended cables with three-to-one internal resonances

Nonlinear planar oscillations of suspended cables subjected to external excitations with three-to-one internal resonances are investigated. At first, the Galerkin method is used to discretize the governing nonlinear integral–partial-differential equation. Then, the method of multiple scales is applied to obtain the modulation equations in the case of primary resonance. The equilibrium solutions, the periodic solutions and chaotic solutions of the modulation equations are also investigated. The Newton–Raphson method and the pseudo-arclength path-following algorithm are used to obtain the frequency/force–response curves. The supercritical Hopf bifurcations are found in these curves. Choosing these bifurcations as the initial points and applying the shooting method and the pseudo-arclength path-following algorithm, the periodic solution branches are obtained. At the same time, the Floquet theory is used to determine the stability of the periodic solutions. Numerical simulations are used to illustrate the cascades of period-doubling bifurcations leading to chaos. At last, the nonlinear responses of the two-degree-of-freedom model are investigated.     

Effets d'une modulation en phase de température à la frontière sur l'instabilité convective d'une couche liquide viscoélastiqueEffects of a temperature modulation in phase at the frontier on the convective instability of a viscoelastic layer

In this Note we study the effects of the temperature modulation, applied at the horizontal boundaries, on the onset of convection of a horizontal liquid Maxwellian layer. It is assumed that the temperature imposed features a steady component and a time dependent component. To analyse the effect of the temperature modulation, the study is restricted to a linear stability analysis. Thus the Floquet theory and a technique of converting a boundary value problem to an initial value problem are used to solve the system of equations corresponding to the onset of convection. Results obtained may be used to characterize the influence of modulation effects and that of the viscoelastic nature of liquid on the critical Rayleigh number. To cite this article: B. Oukada et al., C. R. Mecanique 334 (2006).