Ion and solvent transport in polypyrrole: Experimental test of osmotic model

Ion and solvent transport in the conjugated polymer actuator material, polypyrrole doped with the immobile anion dodecyl benzene sulphonate, has been investigated by simultaneous cyclic voltammetry and Electrochemical Quartz Crystal Microbalance measurements. The purpose was to elucidate the precise nature of the mobile species during redox cycling, and to seek confirmation for the osmotic mechanism of actuation. Three testable aspects of the model were confirmed: The number of inserted H₂O molecules decreases with electrolyte concentration; at the same time the mechanism gradually changes from almost pure cation transport to ca. equal amount of anion transport; exchanging Br⁻ for Cl⁻ ions has only negligible effect at lower concentrations at equal osmotic pressures. Approximately, 4 H₂O molecules are tightly bound to each Na⁺ ion at concentrations <1 M. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Development of a new polymer electrolyte (PMMA-CO-P4VPNO+KClO3) for solid state electrochemical cells

Polymer electrolyte films based on a co-polymer polymethyle methacrylate-co-poly 4vinyl pyridine N-oxide (PMMA-CO-P4VPNO) complexed with KClO₃ were prepared by solution cast technique. The complexation of KClO₃ salt with the polymer was confirmed by infrared studies. Measurements of the dc conductivity in the temperature range 300–410 K and transference numbers were carried out to investigate the charge transport in the polymer electrolyte system. Transference number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. Using the polymer electrolyte solid state electrochemical cells were fabricated with the configuration (K)-(PMMA-CO-P4VPNO+KClO₃)-(I₂+C+electrolyte) and various parameters of the cells including open circuit voltage (OCV) and short circuit current (SCC) were evaluated. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Study of ion–solvent interactions and activation energy of LiBr in DMSO,H<Subscript>2</Subscript>O and DMSO–H<Subscript>2</Subscript>O mixtures at various temperatures

The Jones–Dole B coefficients of the electrolyte Lithium bromide (LiBr), reference salts tetra butyl ammonium tetra phenyl borate (BU₄NBPh₄), tetra butyl ammonium bromide (BU₄NBr), and potassium chloride (KCl) in dimethylsulfoxide (DMSO), water, and DMSO–water mixtures were obtained at different temperatures range from 25 to 45 °C For this, the relative viscosities were measured for Lithium bromide (LiBr) and reference salts in DMSO, water, and DMSO–water mixtures at above-mentioned temperatures. The B coefficients of these electrolytes were behaved as structure makers in DMSO, while in H₂O and DMSO–H₂O mixtures, the B-coefficient values were less positive showing the weak structure-making effect. Ionic viscosity B coefficients allow us to assess the behavior of ions in the solvent mixtures. In this study it was observed that all the values of ionic B coefficient of (Li⁺) were positive and small showing the weak structure-making effects. It was also observed that Br⁻ ions maintain negative B coefficient values in all DMSO–H₂O mixtures, except in 60% DMSO mole fraction. From this it can be concluded that Br⁻ ion behaved as a structure breaker in water and in all DMSO–H₂O mixtures except in 60% DMSO mole fraction mixtures. The low B _± values of alkali metal ions and Br⁻ ions in water are due to the breakdown of the tetrahedral structural of water and the formation of strongly structured solvated ion. It is also observed that the values of the energy of activation of the flow for LiBr are greater in DMSO–water mixtures and in pure water than in DMSO. This may be due the presence of a network of hydrogen bonds which cause the hindrance in the flow of the solution of LiBr in DMSO–water mixtures and in pure water than in DMSO.     

Microhydration of the methylene blue cation in an electrospray ion source

Microhydrated methylene blue cations, MB⁺(H₂O) _n , are produced in an electrospray ion source and their size-distributions are measured as a function of the source temperature. A series of MB⁺(H₂O) _n ions is observed up to n ≃ 60. A striking feature observed in the mass spectra is that the series of hydrated ions starts at n = 4; intensities of n = 1–3 are extremely suppressed. The absence of n = 1–3 ions is well explained by the energetics concerning evaporation processes of water molecules, based on stable structures and the binding energies of MB⁺(H₂O) _n ions calculated by DFT calculations up to n = 5. MB⁺(H₂O) _n ions for n > 4 evaporate a single water molecule sequentially, while MB⁺(H₂O)₄ tends to fragment into MB⁺ and (H₂O)₄ rather than MB⁺(H₂O)₃ and an H₂O molecule. We have observed a clear magic peak at n = 24, which strongly suggests that the MB⁺(H₂O)₂₄ ion is formed by attaching a neutral (H₂O)₂₀ cage onto an MB⁺(H₂O)₄ ion.     

Ionic conductivity and battery characteristic studies on PEO+NaClO3 polymer electrolyte

Solid polymer electrolyte films based on poly (ethylene oxide) PEO complexed with NaClO₃ have been prepared by a solution-cast technique. The solvation of Na⁺ ion with PEO is confirmed by XRD and IR studies. Measurements of the a.c. conductivity in the temperature range 308 – 378 K and the transference numbers have been carried out to investigate the charge transport in this polymer electrolyte system. Transport number data show that the charge transport in this polymer electrolyte system is predominantly due to ions. The highest conductivity (2.12.10⁻⁴ S/cm) has been observed for the 70:30 composition. Using the polymer electrolyte solid state electrochemical cells have been fabricated. The various cell parameters are evaluated and reported.     

Structural and electrical properties of pure and NaBr doped poly (vinyl alcohol) (PVA) polymer electrolyte films for solid state battery applications

A sodium ion conducting polymer electrolyte based on poly (vinyl alcohol) (PVA) complexed with sodium bromide (NaBr) was prepared using solution cast technique. Several experimental techniques such as XRD, FTIR, SEM, temperature-dependant conductivity and transference number measurements have been performed. XRD and FTIR studies confirm the complexation of salt with the polymer. Surface morphology was studied using Scanning Electron Microscopy. DC conductivity was measured in the temperature range of 303–373 K, and the conductivity was found to increase with the increase of dopant concentration as well as temperature. Transference number data suggests that the charge transport in this polymer electrolyte system is mainly due to ions. Using these polymer electrolyte films, electrochemical cells were fabricated with configuration Na/(PVA:NaBr)/V₂O₅ and Na/(PVA:NaBr)/(I2+C+electrolyte) and their discharge characteristics like open circuit voltage (OCV), short circuit current (SCC), power density, energy density were evaluated and compared. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Characterization of a solid state battery based on polyblend of (PVP+PVA+KBrO3) electrolyte

A potassium ion conducting polyblend electrolyte based on polyvinyl pyrrolidone (PVP) + polyvinyl alcohol (PVA) complexed with KBrO₃ was prepared using solution-cast technique. The electrical conductivity and transference number measurements were performed to characterize the polyblend electrolyte for battery applications. These measurements have shown that the electrolyte is a mixed (ionic + electronic) conductor, the charge transport being mainly ionic (t_ion=0.97). Using the electrolyte, electrochemical cells with configurations K / (PVP+PVA+KBrO₃)/(I₂), K / (PVP+PVA+KBrO₃)/(I₂+C) and K/(PVP+PVA+KBrO₃) / (I₂+C+electrolyte) were fabricated and their discharge characteristics studied. The cell with configuration K / (PVP+PVA+KBrO₃) / (I₂+C+electrolyte) exhibited better discharge characteristics than the other configurations. The other cell parameters like open circuit voltage (OCV), short circuit current (SCC) etc. were evaluated and are reported. Paper presented at the 2nd International Conference of Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

REMPI as a tool for studies of OH radicals in catalytic reactions

2 +? O₂→H₂O on polycrystalline Pt foils has been studied by detection of desorbing OH radicals using the Resonance Enhanced Multiphoton Ionization, REMPI, technique. The measurements were performed at catalyst temperatures of 1000–1400 K and a total pressure below 10^-4 mbar. The studies of OH desorption by REMPI were achieved using a two-photon excitation D²Σ^-–X²Π (1–0), followed by one-photon ionization. The ions were detected in a time-of-flight mass spectrometer, TOF-MS, in order to avoid interference from non-resonantly ionized molecules. By applying TOF-MS, a simultaneous non-resonant ionization and detection of H₂, O₂ and H₂O was achieved. Recorded REMPI spectra were compared with spectra simulated using known molecular constants. The kinetics of the reaction derived from the measurements were compared with what was obtained in earlier LIF detection of OH, performed at higher total reactant pressure using the A–X transition. REMPI TOF-MS is shown to be a complement to LIF for reaction studies below 5×10^-4 mbar total pressure, where LIF is too insensitive for quantification. The reaction kinetics was found to be in agreement with a theoretic model and previous LIF studies. Received: 8 March 1996/Revised version: 4 October 1996     

High oxide ion conductivity in Fe and Mg doped LaGaO3 as the electrolyte of solid oxide fuel cells

La(Sr)Ga(Fe,Mg)O₃ exhibited the high oxide ion conductivity and the electrical power generating property of SOFC single cell using La_0.7Sr_0.3Ga_0.7Fe_0.2Mg_0.1O_3-δ (LSGFM) electrolyte was investigated in this study. The transport number of oxide ion is almost 0.8 in LSGFM and so open circuit potential (OCV) is as low as 0.8 V. OCV was strongly affected by anode materials and the highest OCV was achieved on Ni–Fe bimetallic anode. The extremely high power density was achieved by using LSGFM for electrolyte of SOFC. The maximum power densities of the cells can be elevated by coating with oxide ion conductor film at anode side. The maximum power density increased in the following order for coating film: LSGM > SDC > YSZ. The maximum power density of 197 and 100 mW/cm² can be achieved at 873 and 773 K, respectively, when LSGM film deposited on the anode side of LSGFM. Therefore, LSGFM can be used as electrolyte of SOFC operating at intermediate temperature.     

Conductivity studies on PEO:NaClO3 electrolyte system with different plasticizers

A new ion conducting solid polymer electrolyte thin film based on Polyethylene oxide (PEO) with NaClO₃ salt is prepared by solution-casting method. The solvation of salt with PEO has been confirmed by X-ray diffraction and IR spectral studies. Plasticizer effects were studied in PEO:NaClO₃ system by using low molecular weight polyethylene glycol (PEG), dimethyl formamide (DMF) and propylene carbonate(PC). AC conductivity in the temperature range (308–378 K) was measured to evaluate the conductivity of the polymer electrolytes. From the conductivity data, it was found that the conductivity value of pure PEO increases 10²–10⁴ order of magnitude with the addition of salts as well as plasticizers. From the transference number experiments, it was confirmed that the charge transport in these electrolyte is mainly due to the ions (t_ion≈0.94). Finally, the conductivity value of all PEO: NaClO₃ systems were compared.     

Near-infrared diode laser absorption sensor for rapid measurements of temperature and water vapor in a shock tube

A fast-response (100 kHz) tunable diode laser absorption sensor is developed for measurements of temperature and H₂O concentration in shock tubes, e.g. for studies of combustion chemistry. Gas temperature is determined from the ratio of fixed-wavelength laser absorption of two H₂O transitions near 7185.60 cm^-1 and 7154.35 cm^-1, which are selected using design rules for the target temperature range of 1000–2000 K and pressure range of 1–2 atm. Wavelength modulation spectroscopy is employed with second-harmonic detection (WMS-2f) to improve the sensor sensitivity and accuracy. Normalization of the second-harmonic signal by the first-harmonic signal is used to remove the need for calibration and minimize interference from emission, scattering, beam steering, and window fouling. The laser modulation depth for each H₂O transition is optimized to maximize the WMS-2f signal for the target test conditions. The WMS-2f sensor is first validated in mixtures of H₂O and Ar in a heated cell for the temperature range of 500–1200 K (P=1 atm), yielding an accuracy of 1.9% for temperature and 1.4% for H₂O concentration measurements. Shock wave tests with non-reactive H₂O–Ar mixtures are then conducted to demonstrate the sensor accuracy (1.5% for temperature and 1.4% for H₂O concentration) and response time at higher temperatures (1200–1700 K, P=1.3–1.6 atm). PACS 42.62.Fi; 42.55.Px; 42.60.Fc; 07.35.+k     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.     

Selectivity maximization of ethylene epoxidation via NEMCA with zirconia and β″-Al2O3 solid electrolytes

The silver-catalyzed epoxidation of ethylene is a reaction of great technological importance and also represents one of the most challenging and thoroughly studied catalytic systems. It was found that the catalytic activity and selectivity of polycrystalline Ag for the epoxidation and complete oxidation of ethylene can be affected in a pronounced and reversible manner by electrochemically supplying or removing oxygen ions O^2- or Na⁺ to or from the silver catalyst surface in ZrO₂ (8 mol%Y₂O₃) or β″-Al₂O₃ solid electrolyte cell reactors and in the presence or absence of traces of chlorinated hydrocarbons in the gas phase. The steady-state changes in catalytic rates of formation of C₂H₄O and CO₂ are typically 10 to 100 times larger than the corresponding rate of ion transport to or from the catalyst surface, i.e., the reaction exhibits the effect of Non-Faradaic Electrochemical Modification of Catalytic Activity (NEMCA) or “Electrochemical Promotion”. The selectivity to C₂H₄O can be very significantly altered, relative to open circuit conditions. Under fuel rich conditions, temperatures near 250°C and in the presence of traces of 1,2-C₂H₄Cl₂ in the gas phase selectivity values as high as 88% can be obtained, well above the ones reported in the open literature. The observed phenomena are discussed and interpreted within the framework of previous NEMCA studies and the currently prevailing ideas regarding the mechanism of ethylene epoxidation. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994     

Adsorption and reaction of hydrogen sulfide on thin-film cerium oxide

The adsorption and reaction of hydrogen sulfide, H₂S, have been studied on cerium oxide thin films that were vapor deposited on Ru(0 0 0 1). The behavior of the H₂S was examined as a function of Ce oxidation state. H₂S weakly chemisorbs on fully oxidized CeO₂ desorbing near 155 K. Hydrogen from the H₂S reacts with the surface O to desorb as water between 200 K and 450 K. When ca. 20% of the Ce⁴⁺ is reduced to Ce³⁺ more H₂S dissociates to -OH and -SH and water is produced near 580 K. When the ceria is ca. 70% reduced, water formation is suppressed and H₂ desorbs near 580 K. S 2p photoelectron spectroscopy indicates the decomposition of H₂S into -SH and then -S as the sample is annealed from 100 K to 600 K. O 1s photoemission indicated the presence of H₂O and -OH.     

Ionoluminescence studies of combustion synthesized Dy doped nano crystalline forsterite

Ionoluminescence (IL) of nano crystalline Mg₂SiO₄:Dy³⁺ pellet samples bombarded with 100 MeV Si⁺⁸ ions with fluences in the range (1.124–22.480) × 10¹² ions cm⁻² have been studied. Two prominent IL bands with peaks at ∼480 nm and ∼580 nm and a weak band with peak at ∼670 nm are recorded. The characteristic peaks are attributed to luminescence center activated by Dy³⁺ ions due to the transitions ⁴F_9/2→⁶H_15/2,⁶H_13/2 and ⁶H_11/2. It is found that IL intensity initially decreases rapidly and then continuous to decrease slowly with further increase in ion fluence. The reduction in the Ionoluminescence intensity with increase of ion fluence might be attributed to degradation of Si–O ( 2ν₃) bonds present on the surface of the sample and/or due to lattice disorder produced by dense electronic excitation under heavy ion irradiation.     

Synthesis and studies of new plasticized PVP: NaClO3 electrolyte system for battery applications

A new thin film sodium ion conducting plasticized polymer electrolyte based on poly(vinyl pyrrolidone) (PVP) complexed with NaClO₃ salt systems was prepared by the solution-cast method. The interaction of NaClO₃ salt with PVP was confirmed by Infrared (IR) study. Charge transport of these polymer electrolytes is due to ions, which was confirmed by Wagner’s polarization method. From the conductivity measurements, the highest conductivity value 6.71×10⁻⁵ S/cm was observed for the composition PVP:PEG:NaClO₃(30:60:10) at room temperature 35 °C. The redox behaviour and good reversibility of the plasiticized electrolytes are confirmed by electrochemical techniques. Electrochemical cell studies of these polymer electrolytes were analyzed from their discharge characteristics. The open-circuit voltage (OCV) and short-circuit current (SCC) were found to in the range of 2.52 V to 2.36 V and 760 μA to 1040 μA, respectively.     

H2/Pt/Ce0.9Gd0.1O1.95/Pt/O2 fuel cell operated in the intermediate temperature range 500 – 700°C

Ce_0.9Gd_0.1O_1.95 (GCO), is one of the potential candidate electrolytes for intermediate temperature Solid Oxide Fuel Cells (ITSOFC). GCO has high oxide ion conductivity in the intermediate temperature range (500 – 700 °C) compared to other Ce_1−yGd_yO_2-2/y compositions and the Gd³⁺ ion is the most appropriate dopant material compared to other rare earth materials such as Sm³⁺, Y³⁺, Zr³⁺, etc. Our results show that the fuel cell H₂/Pt/Ce_0.9Gd_0.1O_1.95/Pt/O₂ operated in the temperature range 500 – 700°C gives the maximum power densities 0.0049 W/cm² at 500 °C and 0.0126 W/cm² at 650 °C for cell voltages 0.6275 V and 0.6278 V, respectively, where the electrolyte was kept in 5% H₂ (+ Argon) for 12 hours before use in the fuel cell. Maximum power densities are 0.0038 W/cm² at 500 °C and 0.0270 W/cm² at 650 °C for cell voltages 0.5986 and 0.5913 V, respectively, where the electrolyte was kept in 2 % O₂ (+ Argon) for 12 hours before use in the fuel cell. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Effect of ethylene carbonate plasticizer and TiO<Subscript>2</Subscript> nanoparticles on 49% poly(methyl methacrylate) grafted natural rubber-based polymer electrolyte

The effect of plasticizer and TiO₂ nanoparticles on the conductivity, chemical interaction and surface morphology of polymer electrolyte of MG49–EC–LiClO₄–TiO₂ has been investigated. The electrolyte films were successfully prepared by solution casting technique. The ceramic filler, TiO₂, was synthesized in situ by sol-gel process and was added into the MG49–EC–LiClO₄ electrolyte system. Alternating current electrochemical impedance spectroscopy was employed to investigate the ionic conductivity of the electrolyte films at 25 °C, and the analysis showed that the addition of TiO₂ filler and ethylene carbonate (EC) plasticizer has increased the ionic conductivity of the electrolyte up to its optimum level. The highest conductivity of 1.1 × 10⁻³ Scm⁻¹ was obtained at 30 wt.% of EC. Fourier transform infrared spectroscopy measurement was employed to study the interactions between lithium ions and oxygen atoms that occurred at carbonyl (C=O) and ether (C-O-C) groups. The scanning electron microscopy micrograph shows that the electrolyte with 30 wt.% EC posses the smoothest surface for which the highest conductivity was obtained.