The effect of composition,electron irradiation and quenching on ionic conductivity in a new solid polymer electrolyte: (PEG)<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NH<Subscript>4</Subscript>I

We have prepared, characterized and investigated a new PEG-2000 based solid polymer electrolyte (PEG) _x NH₄I. Ionic conductivity measurements have been made as a function of salt concentration as well as temperature in the range 265–330 K. Selected compositions of the electrolyte were exposed to a beam of 8 MeV electrons to an accumulated dose of 10 kGy to study the effect on ionic conductivity. The electrolyte samples were also quenched at liquid nitrogen temperature and conductivity measurements were made. The ionic conductivity at room temperature exhibits a characteristic double peak for the composition x = 20 and 70. Both electron beam irradiation and quenching at low temperature have resulted in an increase in conductivity by 1–2 orders of magnitude. The enhancement of conductivity upon irradiation and quenching is interpreted as due to an increase in amorphous region and decrease in crystallinity of the electrolyte. DSC and proton NMR measurements also support this conclusion.      

Theoretical determination of the magnetic properties of 2-pyrone and 4-pyrone,and o-benzoquinone and p-benzoquinone

A series of theoretical procedures, relying on the conventional common-origin and distributed-origin approaches, and adopting extended gaugeless as well as London basis sets, have been applied at the Hartree-Fock level of accuracy to predict magnetic susceptibilities and nuclear magnetic shieldings of four molecular systems that aroused particular interest and discussion concerning their aromatic character. The theoretical results are of near Hartree-Fock quality. Comparison with experimental values for magnetic susceptibilities seems to indicate that the latter need to be revised. Analysis of calculated properties and of plots of current density induced by the magnetic field in the π-electrons provides simple and effective tools for the classification of 2- and 4-pyrones, and o- and p-benzoquinone as non-aromatic.     

Performance of lithium-ion cells using 1 M LiPF<Subscript>6</Subscript> in EC/DEC (<Emphasis Type="Italic">v</Emphasis>/<Emphasis Type="Italic">v</Emphasis> = 1/2) electrolyte with ethyl propionate additive

In this work, 1 M LiPF₆:EC:DEC (v/v = 1/2) was used as a baseline electrolyte where EC is ethylene carbonate and DEC is diethyl carbonate. Ethyl propionate (EP) was used as an additive. The conductivity of the liquid electrolyte was obtained at ambient and elevated temperatures. The highest room temperature conductivity was observed at (8.05 ± 0.16) mS cm⁻¹ for the electrolyte containing 28.6 vol.% EP. Viscosity of the baseline and EP added baseline electrolytes have been measured at room and elevated temperatures. The electrolyte was also characterized by linear sweep voltammetry. The highest conducting electrolyte with 28.6 vol.% EP and the baseline electrolyte were used to fabricate several batteries. The batteries were charged and discharged at room temperature and at −20°C.     

On the interfacial capacitance of an electrolyte at a metallic electrode around zero surface charge

The behaviour of the capacitance of a planar double layer containing a restricted primitive model electrolyte (equi-sized rigid ions moving in a continuum dielectric) at and around zero surface charge is examined for a polarizable electrode with particular emphasis on a metallic surface. Capacitance results are reported for symmetric valency (1:1) salts encompassing a range of concentrations and temperatures covering both electrolyte solution and ionic liquid regimes. Although the modified Poisson–Boltzmann theory is principally employed, at higher concentrations the theoretical calculations have been supplemented by Monte Carlo simulations. Capacitance anomaly, that is, increase of capacitance with temperature at low temperatures, is seen to occur when the electrode is an insulator with a low dielectric constant or when it is unpolarized. No capacitance anomaly is, however, seen for a metallic electrode with an infinite dielectric constant and in this situation the capacitance increases (a) dramatically at low temperatures (strong coupling) at a given concentration, and (b) as concentration increases at a given temperature. These capacitance trends are consistent with earlier works in the presence or absence of surface polarization and, in particular, the results for a conducting electrode at ionic liquid concentrations are consistent with that recently reported by Loth et al. [Phys. Rev. E, 82, 056102 (2010)]. Overall the theoretical predictions are qualitative to semi-quantitative with the simulations.     

Photoelectrolysis of water with semiconductors

The use of semiconductors, as photoelectrodes in electrolytic cells for the electrolysis of water, is described and the results reported in the literature for various semiconductors are reviewed. The most important properties of the semiconductor are shown to be the band-gap energyE _g , and the flat-band potentialU _fb . The semiconductor absorbs photons that are more energetic than the band-gap energy and creates electronhole pairs. These charge carriers can be separated before recombination by the electric field at the semiconductor-electrolyte interface. For electrolysis to proceed, the potential corresponding to the band gap must appreciably exceed the standard potential for the electrolysis of water, 1.23 volts. In addition, the flat-band potential must be more negative than the hydrogen potential or an external bias voltage is required. The semiconductor must not corrode under the operating conditions and must permit transfer of the minority carrier to the electrolyte. The current theories of charge transfer and reaction mechanism are discussed. Many semiconductive oxides have been tested as photoanodes and found to be stable. However, only those compounds that have band gaps of ca. 3 eV have been found to have flat-band potentials that are more negative than the hydrogen potential. These compounds will electrolyse water, without additional bias voltage, but are inefficient absorbers of solar energy. Experiments withp-type photocathodes,p andn combinations and various special configurations are also described. The paper concludes with a general discussion of the practical prospects of photoelectrolysis in comparison with solid-state solar cells.     

Application of a radioactive tracer method for diffusion study in some liquids

In this paper a radioactive tracer technique based on sliding cell method developed in our laboratory for the study of diffusion in liquids is presented in detail. This method consists of radioactive and non-radioactive liquid columns of equal length and the radiation detector is placed in a vertical geometry over the diffusion column. Some liquid metals and aqueous electrolyte solutions were studied by this method. The data of liquid metals like mercury and gallium have been analyzed from the point of view of hard sphere model and those of electrolyte solutions from phenomenological theories. Onsager’s coefficientsL ₁₁,L ₁₂,L ₂₂ have been calculated from the experimental data and the variation of diffusion with solute concentration has been explained from ion-ion interaction.     

Quasi-molecular resonances in muonic charge-exchange reactions

We present the first thorough theoretical discussion of non-monotonic structure in the temporal behavior of X-ray fluorescence intensity spectra of muon charge-exchange reactions of the type pμ + Z→p + μZ. Our discussion is based on semiclassical methods; our results are almost entirely analytical. We find that the reported experimental maxima of muon charge-exchange rates are very close to the theoretical limits. We identify a new quantum mechanism, quantum impedance matching, which explains observed inelastic transitions close to the Unitarity Limit. We investigate the specific example of the reaction pμO ^{8 +} in detail using two-center Coulomb adiabatic potential terms. We find that quantum impedance matched higher-order partial-wave resonances yielding muon-transfer rates close to the Unitarity Limit are responsible for the remarkable non-monotonic structure in the X-ray fluorescence spectra. Received 7 January 2002 / Received in final form 15 April 2002 Published online 24 September 2002     

Theory and simulation of electrolyte mixtures

Monte Carlo simulation and theoretical results on some aspects of thermodynamics of mixtures of electrolytes with a common species are presented. Both charge symmetric mixtures, where ions differ only in size, and charge asymmetric but size symmetric mixtures at ionic strength ranging generally from I = 10^?4 to 1.0 M, and in a few cases up to I = 2 M, are examined. The theoretical methods explored are: (i) the symmetric Poisson-Boltzmann theory, (ii) the modified Poisson-Boltzmann theory and (iii) the hypernetted-chain integral equation. The first two electrolyte mixing coefficients w ₀ and w ₁ of the various mixtures are calculated from an accurate determination of their osmotic pressure data. The theories are seen to be consistent among themselves, and with certain limiting laws in the literature, in predicting the trends of the mixing coefficients with respect to ionic strength. Some selected relevant experimental data have been analysed and compared with the theoretical and simulation trends. In addition the mean activity coefficients for a model mimicking the mixture of KC1 and KF electrolytes are calculated and hence the Harned coefficients obtained for this system. These calculations are compared with the experimental data and Monte Carlo results available in the literature. The theoretically predicted Harned coefficients are in good agreement with the simulation results for the model KC1-KF mixture.     

Series resistance calculation for the Metal-Insulator-Semiconductor Schottky barrier diodes

An accurate way of determining the series resistance R_s of Schottky Barrier Diodes (SBDs) with and without the interfacial oxide layer using forward current-voltage (I–V) characteristics is discussed both theoretically and experimentally by taking into account the applied voltage drop across the interfacial layerV _i. For the experimental discussion, the forward biasI–V characteristics of the SBDs with and without the oxide layer fabricated by LEC (the Liquid-Encapsulated Czochralski) GaAs were performed. The SBD without the oxide layer was fabricated to confirm a novel calculation method. For the theoretical discussion, an expression ofV _i was obtained by considering effects of the layer thickness and the interface state density parameters on forward biasI–V of the SBDs. The valueR _s of the SBD with interfacial oxide layer was seen to be larger than that of the SBD without the interfacial oxide layer due to contribution of this layer to the series resistance. According to the obtained theoretical formula, the value ofV _i for the SBD with the oxide layer was calculated and it was subtracted from the applied voltage values V and then the value ofR _s was recalculated. Thus, it has been shown that this new value ofR _s is in much closer agreement with that determined for the SBD without the oxide layer as predicted. Furthermore, the curves of the interface states energy distribution of each sample are determined. It was concluded that the shape of the density distribution curve and order of magnitude of the density of the interface states in the considered energy range are in close agreement with those obtained by others for Au/n-GaAs Schottky diodes by Schottky capacitance spectroscopy.     

All-solid-state lithium-based polymer cells for high-temperature applications

A lithium salt doped siloxane/methacrylate copolymer membrane, prepared by a rapid UV curing process, has been characterised and tested as a fully solid electrolyte in rechargeable lithium test cells using low cost materials as electrodes. In addition, results of a laboratory-scale Li-ion polymer cell, assembled by contacting a LiFePO₄ cathode with a graphite anode and using the solid polymer as electrolyte, are presented. The polymer electrolyte production process is simple and versatile and the highly cross-linked membrane demonstrates mechanical integrity, low T _g and large thermal stability. It is an extra soft, non-crystalline, transparent solid and shows sufficient ionic conductivity (>10⁻⁴ S cm⁻¹ at 60 °C) along with a wide electrochemical stability window and improved interfacial stability with respect to lithium. The performances in Li-based cells have been determined by cycling tests carried out at 80 °C. Good rate capability, along with high charge/discharge efficiency even at 1C-rate, and a satisfactory cyclability have been obtained. These results outline the practical relevance of the use of this solid electrolyte membrane (which serves as the separator simultaneously) in Li-based cells conceived for high-temperature applications.     

Dynamics of formation of the mosaic structure of porous silicon during prolonged anodic etching in electrolytes with an internal current source

The spontaneous self-organization of a porous surface mosaic structure in the form of islands of oxidized por-Si nanocrystallites separated by silicon ledges has been observed during prolonged anodic etching of p-Si (100) in electrolytes with an internal current source. The por-Si mosaic structure is spontaneously formed as a result of relaxation of an elastically strained layer of the porous surface. The self-organization of the mosaic structure of the por-Si surface, island sizes, and the period of their arrangement are controlled by a number of factors arising in the complex heterophase system electrolyte/por-Si/c-Si/during etching, i.e., the spatio-temporal distribution of point defects of interstitials I _Si and vacancies V _Si in the c-Si surface region, the formation of capillary fluctuation forces at the electrolyte/por-Si/c-Si/interface, the elastic deformation forces induced by the lattice parameter mismatch between the oxidized por-Si nanocrystallites and the c-Si matrix. The conditions responsible for the manifestation of these forces depend on the self-consistent parameters of etching of the complex heterophase electrochemical system electrolyte/por-Si/c-Si/with an internal current source, including the electrode characteristics and cell parameters.     

Investigation on compositional effect of PEG:BaTiO<Subscript>3</Subscript> in plasticized PVC–LiBETi polymer composite electrolytes

The blend-based polymer electrolyte comprising poly(vinyl chloride) (PVC) and poly(ethylene glycol) (PEG) as host polymer and lithium bis(perfluoroethanesulfonyl)imide as complexing salt have been prepared. Ethylene carbonate and dimethyl carbonate (50:50 v/v) are used as plasticizer for the system. The barium titanate is used as a filler, and the ratio of (PEG:BaTiO₃) is varied to study its effect on the conductivity behavior of the electrolyte. XRD and ac impedance studies are carried out on the prepared samples. The ac impedance measurements show that the conductivity of the prepared samples depends on the (PEG:BaTiO₃) ratio, and its value is higher for (15:5) wt.% of (PEG:BaTiO₃)-incorporated film. The temperature dependence of the conductivity of the polymer films obeys VTF relation. The role of ferroelectric filler in enhancing the conductivity is studied. The thermal stability of the film is ascertained from TG/DTA studies. The phase morphological study reveals that the porous nature of the polymer electrolyte membranes depends on the (PEG:BaTiO₃) ratio.     

Bifurcation analysis of Liesegang ring pattern formation

Bifurcation analysis is introduced to a prototype Liesegang ring (LR) model to explain pattern formation as an instability of a propagating plane reaction front. A theoretical criterion for the onset of patterning is derived and numerically tested. The uneven spacing law of LR bands is explained as a consequence of the time varying velocity of the moving reaction front. Suggestions for controlling pattern formation are provided.     

Mixed cation effect and iodide ion conductivity in electrolytes for dye sensitized solar cells

Dye-sensitized solar cells (DSSCs) offer an alternative to conventional silicon solar cell because of low cost and easy fabrication. However, one major drawback in DSSCs is their low efficiency. This paper reports the effect of using a binary iodide salt mixture with different size cations on the efficiency enhancement in dye sensitized solar cells based on polymer gel electrolytes. Several different polymers, such as polyacrylonitrile (PAN), polymethylmethacrylate (PMMA), poly (vinylidenefluoride (PVdF)), and polyethylene oxide (PEO) have been used as host polymers. A binary iodide mixture consisting of an alkaline iodide salt (small cation) and a quaternary ammonium iodide salt such as tetrapropyl ammonium iodide (Pr₄NI) (large cation) has been used as the iodide ion source. In some of these systems, efficiency enhancement of more than 25% has been reached due to the “mixed cation effect”. From these studies, it was established that the variation of the power conversion efficiency with the concentration ratio of the two iodide salts follows the same trend as the short circuit current density (J _sc) and goes through a maximum at a particular salt concentration ratio. The maximum efficiency was found to be higher than the efficiencies of the DSSCs with only a single iodide salt in the electrolyte. The J _sc in these DSSCs appears to be governed by the iodide ion conductivity of the gel electrolyte. The observed efficiency enhancement has been explained on the basis of the electrode effects as well as electrolyte effects where the cations play a dominant role.

     

A non-empirical LCAO MO SCF and experimental investigation on the core-ionized states of acetylacetone and some of its enol tautomers

Non-empirical LCAO MO SCF calculations have been performed on the ground and core-hole states of acetylacetone for a range of geometries. The theoretical studies have been complemented by gas-phase ESCA studies of both the O 1s and C 1s core levels. A comparison of the theoretical and experimental data shows excellent agreement for an unsymmetrical Cs enol structure and a discussion is given of the low-energy shake-up satellites accompanying both C 1s and O 1s core ionization. Consideration is also given to the relative energies of the various tautomeric model systems as a function of the hole states.     

Solid polymeric electrolyte of PVC–ENR–LiClO<Subscript>4</Subscript>

The ionic conductivity of PVC–ENR–LiClO₄ (PVC, polyvinyl chloride; ENR, epoxidized natural rubber) as a function of LiClO₄ concentration, ENR concentration, temperature, and radiation dose of electron beam cross-linking has been studied. The electrolyte samples were prepared by solution casting technique. Their ionic conductivities were measured using the impedance spectroscopy technique. It was observed that the relationship between the concentration of salt, as well as temperature, and conductivity were linear. The electrolyte conductivity increases with ENR concentration. This relationship was discussed using the number of charge carrier theory. The conductivity–temperature behaviour of the electrolyte is Arrhenian. The conductivity also varies with the radiation dose of the electron beam cross-linking. The highest room temperature conductivity of the electrolyte of 8.5 × 10⁻⁷ S/cm was obtained at 30% by weight of LiClO₄. The activation energy, E _a and pre-exponential factor, σ _o, are 1.4 × 10⁻² eV and 1.5 × 10⁻¹¹ S/cm, respectively.     

X‐ray Raman spectroscopy of lithium‐ion battery electrolyte solutions in a flow cell

The effects of varying LiPF₆ salt concentration and the presence of lithium bis(oxalate)borate additive on the electronic structure of commonly used lithium‐ion battery electrolyte solvents (ethylene carbonate–dimethyl carbonate and propylene carbonate) have been investigated. X‐ray Raman scattering spectroscopy (a non‐resonant inelastic X‐ray scattering method) was utilized together with a closed‐circle flow cell. Carbon and oxygen K‐edges provide characteristic information on the electronic structure of the electrolyte solutions, which are sensitive to local chemistry. Higher Li⁺ ion concentration in the solvent manifests itself as a blue‐shift of both the π* feature in the carbon edge and the carbonyl π* feature in the oxygen edge. While these oxygen K‐edge results agree with previous soft X‐ray absorption studies on LiBF₄ salt concentration in propylene carbonate, carbon K‐edge spectra reveal a shift in energy, which can be explained with differing ionic conductivities of the electrolyte solutions.     

Pyroelectric detection of a CO2 laser beam using organic copolymers

Pyroelectric detection of a CO₂ laser beam has been investigated by using organic copolymers such as VDF/TrFE- and VDCN/VAc copolymers, and compared with that of PVDF polymer. The voltage responsitiviesR _v are 40 mV/W for VDF/TrFE and 2 mV/W for VDCN/VAc at room temperature and at a chopping frequency of 200 Hz. (For comparison, the value of PVDF is 20 mV/W.) From the frequency dependence of the detected output, the electric time constant _E is evaluated to be about 6.4 ms and 2.6 ms for the former and latter copolymers with the detection area 3×3 mm², respectively. Some theoretical discussion is also given of the responsivity, frequency dependence and temperature dependence obtained.     

On the growth of gadolinia-doped ceria by pulsed laser deposition

In order to establish a new platform to manufacture micro-sized solid oxide fuel cells (SOFCs) with low operating temperatures, new design concepts, new preparation methods and new materials are being explored. Our studies in this paper are focused on the electrolyte material, and in particular gadolinia doped ceria (GDC), an electrolyte material, likely to replace the traditional yttria-stabilised zirconia (YSZ) for low temperature applications. GDC films were grown on a single crystal Si by pulsed laser deposition (PLD). The microstructure of the films as a function of growth time has been studied. We have found that the mean grain size increases with film thickness h as h^2/5, in agreement with theoretical results.     

Solute reaction mediated precipitate patterns in cross gradient free systems

Recent studies on the spontaneous formation of undulatory patterns of precipitate concentration, such as Liesegang and related phenomena, have shown that these effects can be explained on the basis of a competitive particle growth mechanism as underlies Ostwald ripening. However these effects require an overall gradient or boundary perturbation to induce regular patterning on a scale greater than the interparticle spacing to override the single crystal-so called greedy giant instability. Here we show that by allowing for precipitate particle mediated reactions involving the solute species (from which the precipitate is constructed) a fastest growing mode of wave vectork _d , 0<k _d <, exists and thus pattern formation can occur completely autonomously at a well defined wave length without the need of cross gradients. These processes may be much more widely realized in physical and biological self organization processes than the familiar reaction diffusion (Turing) model due to the rather nonspecific nature of the present phenomenon.Research supported in part by grants from the National Science Foundation and the Petroleum Research FundA.P. Sloan Fellow, 1980–82NATO Fellow, 1982