Brillouin Scattering Investigation of Solvation Dynamics in Succinonitrile-Lithium Salt Plastic Crystalline Electrolytes

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans-gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO(4) samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO(4) (similar to 0.3-1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (''compactness''). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as nu(f)) as the temperature decreases. Anomalous temperature dependent behavior of nu(f) with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes.

Applications of solid electrolytes in galvanic sensors

The concepts and theoretical origins of conduction domains for solid electrolytes and electrode polarization are outlined briefly. The point electrode made of the ' solid electrolyte material is useful for deflecting the semipermeability flux away from the electrode. The emf of galvanic sensors consisting of two solid electrolytes in intimate contact with each other and in which transport occurs by a common ion is reviewed. The voltage of such cells depends on the chemical potential of the active species at the interface between the two electrolytes, which can be evaluated from the transport properties of electrolytes using a numerical procedure. The factors governing the speed of response of solid electrolyte gas sensors are analyzed. A rigorous expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for nonisothermal galvanic sensors are outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. The principles of operation of galvanic sensors for oxygen, sulphur, oxides of sulphur (SOx,x=2,3), carbon, oxides uf carbon (COx,x= 1,2), oxides of nitrogen (NOx,x= 1,2) and silicon are discussed. The use of auxiliary electrodes in galvanic sensors to expand the detection capability of known solid electrolytes to a large number of species is explained with reference to sensors for sulphur and oxides of sulphur (SOx,x=2,3).Finally the cause of the common errors in galvanic measurements and test for the correct functioning of galvanic sensors is given.

Application of composition gradient solid electrolytes in sensors and thermodynamic measurements

New compos~tiong radient solid electrolytes are developed which have application in high temperature solid state galvanic sensors and provide a new tool for thermodynamic measurements. The electrolyte consists oi a solid solution between two ionic conductors with a common mobile ion and spatial variation in composition of otber coxup nents. Incorporation of the composite electrolyte in sensors permits the use oi dissimilar gas electrodes. It is demonsuated, both experimentall y and theoretically, that the composition gradient of the relativeiy immobile species does not give rise to a diffusion potential.The emi of a cell is determined by the activity of the mobile species at the two eiectrodes. The thermodynamic properties of solid solutions can be measured using the gradient solid electrolyte. The experimental stuay is based on model systems A?(COj)x(S04)l-x (A=Na,K),where S \.aria across the electrolyte. The functionally gradient solid electrolytes used for activity measurements consist of pure carbonate at one ena and the solid solution under stuav at the other. The identical vaiues of activity, obtained h m t hree different modes of operation of the ceil. indicate unit transport number for the ddi metal ion in the graciient electrolyte. Tlle activities in the solid solutions exhibit moderate positive deviations from Raoult 's law.

Subspace-based DOA estimation using Fractional Lower Order statistics

Direction Of Arrival (DOA) estimation, using a sensor array, in the presence of non-Gaussian noise using Fractional Lower-Order Moments (FLOM)matrices is studied. In this paper, a new FLOM based technique using the Fractional Lower Order Infinity Norm based Covariance (FLIC) Matrix is proposed. The bounded property and the low-rank subspace structure of the FLIC matrix is derived. Performance of FLIC based DOA estimation using MUSIC, ESPRIT, is shown to be better than other FLOM based methods.

Microscopic study of the 2/5 fractional quantum Hall edge

This paper reports on our study of the edge of the 2/5 fractional quantum Hall state, which is more complicated than the edge of the 1/3 state because of the presence of edge sectors corresponding to different partitions of composite fermions in the lowest two Lambda levels. The addition of an electron at the edge is a nonperturbative process and it is not a priori obvious in what manner the added electron distributes itself over these sectors. We show, from a microscopic calculation, that when an electron is added at the edge of the ground state in the [N(1), N(2)] sector, where N(1) and N(2) are the numbers of composite fermions in the lowest two Lambda levels, the resulting state lies in either [N(1) + 1, N(2)] or [N(1), N(2) + 1] sectors; adding an electron at the edge is thus equivalent to adding a composite fermion at the edge. The coupling to other sectors of the form [N(1) + 1 + k, N(2) - k], k integer, is negligible in the asymptotically low-energy limit. This study also allows a detailed comparison with the two-boson model of the 2/5 edge. We compute the spectral weights and find that while the individual spectral weights are complicated and nonuniversal, their sum is consistent with an effective two-boson description of the 2/5 edge.

Ion Transport in Liquid Salt Solutions with Oxide Dispersions:``Soggy Sand'' Electrolytes

``Soggy sand'' electrolyte, which essentially consists of oxide dispersions in nonaqueous liquid salt solutions, comprises an important class of soft matter electrolytes. The ion transport mechanism of soggy sand electrolyte is complex. The configuration of particles in the liquid solution has been observed to depend in a nontrivial manner on various parameters related to the oxide (concentration, size, surface chemistry) and solvent (dielectric constant, viscosity) as well as time. The state of the particles in solution not only affects ionic conductivity but also effectively the mechanical and electrochemical properties of the solid liquid composite. Apart from comprehensive understanding of the underlying phenomena that govern ion transport, which will benefit design of better electrolytes, the problem has far-reaching implications in diverse fields such as catalysis, colloid chemistry, and biotechnology.

Chitosan-polyvinyl alcohol-sulfonated polyethersulfone mixed-matrix membranes as methanol-barrier electrolytes for DMFCs

Chitosan (CS)-polyvinyl alcohol (PVA) cross-linked with sulfosuccinic acid (SSA) and modified with sulfonated polyethersulfone (SPES) mixed-matrix membranes are reported for their application in direct methanol fuel cells (DMFCs). Polyethersulfone (PES) is sulfonated by chlorosulfonic acid and factors affecting the sulfonation reaction, such as time and temperature, are studied. The ion-exchange capacity, degree of sulfonation, sorption, and proton conductivity for the mixed-matrix membranes are investigated. The mixed-matrix membranes are also characterised for their mechanical and thermal properties. The methanol-crossover flux across the mixed-matrix membranes is studied by measuring the mass balance of methanol using the density meter. The methanol cross-over for these membranes is found to be about 33% lower in relation to Nafion-117 membrane. The DMFC employing CS-PVA-SPES mixed-matrix membrane with an optimum content of 25 wt % SPES delivers a peak power-density of 5.5 mW cm-2 at a load current-density of 25 mA cm-2 while operating at 70 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

An Accurate Fractional Period Delay Generation System

An all-digital technique is proposed for generating an accurate delay irrespective of the inaccuracies of a controllable delay line. A subsampling technique-based delay measurement unit (DMU) capable of measuring delays accurately for the full period range is used as the feedback element to build accurate fractional period delays based on input digital control bits. The proposed delay generation system periodically measures and corrects the error and maintains it at the minimum value without requiring any special calibration phase. Up to 40x improvement in accuracy is demonstrated for a commercial programmable delay generator chip. The time-precision trade-off feature of the DMU is utilized to reduce the locking time. Loop dynamics are adjusted to stabilize the delay after the minimum error is achieved, thus avoiding additional jitter. Measurement results from a high-end oscilloscope also validate the effectiveness of the proposed system in improving accuracy.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

An EQCM investigation of capacitance of MnO2 in electrolytes containing multivalent cations

MnO2 is electrochemically deposited on Au coated quartz crystal to study the electrochemical capacitance properties and to monitor the mass variations that accompany reversible adsorption/desorption of Na+, Mg2+ and La3+ ions during discharge/charge cycling. There is an increase in the values of specific capacitance of MnO2 with increase in charge of the cation in the electrolyte. Also, there is an increase in mass during discharge due to adsorption of cations from the electrolyte resulting from reduction of MnO2. Mass decreases during charging process due to desorption of cations. The magnitude of mass variation is approximately proportional to the atomic weight of the cationic element. (C) 2012 Elsevier B.V. All rights reserved.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Fractional Hilbert transform extensions and associated analytic signal construction

The analytic signal (AS) was proposed by Gabor as a complex signal corresponding to a given real signal. The AS has a one-sided spectrum and gives rise to meaningful spectral averages. The Hilbert transform (HT) is a key component in Gabor's AS construction. We generalize the construction methodology by employing the fractional Hilbert transform (FrHT), without going through the standard fractional Fourier transform (FrFT) route. We discuss some properties of the fractional Hilbert operator and show how decomposition of the operator in terms of the identity and the standard Hilbert operators enables the construction of a family of analytic signals. We show that these analytic signals also satisfy Bedrosian-type properties and that their time-frequency localization properties are unaltered. We also propose a generalized-phase AS (GPAS) using a generalized-phase Hilbert transform (GPHT). We show that the GPHT shares many properties of the FrHT, in particular, selective highlighting of singularities, and a connection with Lie groups. We also investigate the duality between analyticity and causality concepts to arrive at a representation of causal signals in terms of the FrHT and GPHT. On the application front, we develop a secure multi-key single-sideband (SSB) modulation scheme and analyze its performance in noise and sensitivity to security key perturbations. (C) 2013 Elsevier B.V. All rights reserved.

Cubic Sieve Congruence of the Discrete Logarithm Problem, and fractional part sequences

The Cubic Sieve Method for solving the Discrete Logarithm Problem in prime fields requires a nontrivial solution to the Cubic Sieve Congruence (CSC) x(3) equivalent to y(2)z (mod p), where p is a given prime number. A nontrivial solution must also satisfy x(3) not equal y(2)z and 1 <= x, y, z < p(alpha), where alpha is a given real number such that 1/3 < alpha <= 1/2. The CSC problem is to find an efficient algorithm to obtain a nontrivial solution to CSC. CSC can be parametrized as x equivalent to v(2)z (mod p) and y equivalent to v(3)z (mod p). In this paper, we give a deterministic polynomial-time (O(ln(3) p) bit-operations) algorithm to determine, for a given v, a nontrivial solution to CSC, if one exists. Previously it took (O) over tilde (p(alpha)) time in the worst case to determine this. We relate the CSC problem to the gap problem of fractional part sequences, where we need to determine the non-negative integers N satisfying the fractional part inequality {theta N} < phi (theta and phi are given real numbers). The correspondence between the CSC problem and the gap problem is that determining the parameter z in the former problem corresponds to determining N in the latter problem. We also show in the alpha = 1/2 case of CSC that for a certain class of primes the CSC problem can be solved deterministically in <(O)over tilde>(p(1/3)) time compared to the previous best of (O) over tilde (p(1/2)). It is empirically observed that about one out of three primes is covered by the above class. (C) 2013 Elsevier B.V. All rights reserved.

A fractional order proportional integral controller for path following and trajectory tracking of miniature air vehicles

In this paper, a fractional order proportional-integral controller is developed for a miniature air vehicle for rectilinear path following and trajectory tracking. The controller is implemented by constructing a vector field surrounding the path to be followed, which is then used to generate course commands for the miniature air vehicle. The fractional order proportional-integral controller is simulated using the fundamentals of fractional calculus, and the results for this controller are compared with those obtained for a proportional controller and a proportional integral controller. In order to analyze the performance of the controllers, four performance metrics, namely (maximum) overshoot, control effort, settling time and integral of the timed absolute error cost, have been selected. A comparison of the nominal as well as the robust performances of these controllers indicates that the fractional order proportional-integral controller exhibits the best performance in terms of ITAE while showing comparable performances in all other aspects.

Ag nanoparticles-anchored reduced graphene oxide catalyst for oxygen electrode reaction in aqueous electrolytes and also a non-aqueous electrolyte for Li-O-2 cells

Silver nanoparticles-anchored reduced graphene oxide (Ag-RGO) is prepared by simultaneous reduction of graphene oxide and Ag+ ions in an aqueous medium by ethylene glycol as the reducing agent. Ag particles of average size of 4.7 nm were uniformly distributed on the RGO sheets. Oxygen reduction reaction (ORR) is studied on Ag-RGO catalyst in both aqueous and non-aqueous electrolytes by using cyclic voltammetry and rotating disk electrode techniques. As the interest in non-aqueous electrolyte is to study the catalytic performance of Ag-RGO for rechargeable Li-O-2 cells, these cells are assembled and characterized. Li-O-2 cells with Ag-RGO as the oxygen electrode catalyst are subjected to charge-discharge cycling at several current densities. A discharge capacity of 11 950 mA h g(-1) (11.29 mA h cm(-2)) is obtained initially at low current density. Although there is a decrease in the capacity on repeated discharge-charge cycling initially, a stable capacity is observed for about 30 cycles. The results indicate that Ag-RGO is a suitable catalyst for rechargeable Li-O-2 cells.