Studies on the structural and ionic transport properties at elevated temperatures of La1-xMnO3 +/-delta synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La1-xMnO3 (X=0.0-0.18) compositions. Powders annealed in oxygen/air at 1000-1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173-1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm(-1) at 298 K to 105 S cm(-1) at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0X10(-6) S cm(-1) at 700 K to 2.0X10(-3) S cm(-1) at 1273 K. The ionic transference number of these compositions ranges from 3.0X10(-5) to 5.0X10(-5) at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03-1.10 and 0.80-1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV. (C) 2002 Elsevier Science B.V. All rights reserved.

Utilizing an ionic liquid for synthesizing a soft matter polymer ``gel'' electrolyte for high rate capability lithium-ion batteries

A cross-linked polymer ``gel'' electrolyte obtained from free radical polymerization of a vinyl monomer (acrylonitrile; AN) in a room temperature ionic liquid electrolyte (N,N-methyl butyl pyrrolidinium-bis (trifluoromethanesulphonyl)imide-lithium bis(trifluoromethanesulphonyl) imide;LiTFSI-[Py(1,4)-TFSI]) for application in high rate capability rechargeable lithium-ion batteries is discussed here. This is a novel alternative compared to the often employed approach of using a molecular liquid as the medium for performing the polymerization reaction. The polymer ``gel'' electrolytes (AN:Py(1,4)-TFSI = 0.16-0.18, w/w) showed remarkable compliable mechanical strength and higher thermal stability compared to LiTFSI-[Py(1,4)-TFSI]. Despite two orders increase in magnitude of viscosity of polymer ``gels'', the room temperature ionic conductivity of the ``gels'' (1.1 x 10(-3)-1.7 x 10(-3) Omega(-1) cm(-1)) were nearly identical to that of the ionic liquid (1.8 x 10(-3) Omega(-1) cm(-1)). The present ``gel'' electrolytes did not exhibit any ageing effects on ionic conductivity similar to the conventional polymer gel electrolytes (e.g. high molecular weight polymer + salt + high dielectric constant molecular solvent). The disorder (ionic liquid) to a relative order (cross-linked polymer electrolyte) transformation does not at all influence the concentration of conducting species. The polymer framework is still able to provide efficient pathways for fast ion transport. Unlike the ionic liquid which is impossible to assemble without a conventional separator in a cell, the polymer ``gel'' electrolyte could be conveniently assembled without a separator in a Li vertical bar lithium iron phosphate (LiFePO(4)) cell. Compared to the ionic liquid, the ``gel'' electrolyte showed exceptional cyclability and rate capability (current density: 35-760 mA g(-1) with LiFePO(4) electronically wired with carbon (amorphous or multiwalled nanotube [MWCNT]).

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

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.

Conductivity Studies of Silver-, Potassium-, and Magnesium-Doped Hydroxyapatite

We report the electrical transport properties of silver-, potassium-, and magnesium-doped hydroxyapatites (HAs). While Ag+ or K+ doping to HA enhances the conductivity, Mg+2 doping lowers the conductivity when compared with undoped HA. The mechanism behind the observed differences in ionic conductivity has been discussed using the analysis of high-temperature frequency-dependent conductivity data, Cole-Cole plots of impedance data as well as on the basis of the frequency dependence of the imaginary part (M) of the complex electric modulus. The f(max) of modulus M decreased in silver- and potassium-doped samples in comparison with the undoped HA.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Fast densification and electrical conductivity of yttria-stabilized zirconia nanoceramics

Nanocrystalline 8YSZ (8 mol% yttria stabilized zirconia) bulk samples with grain sizes of 20-30 nm were synthesized by Sol-Gel method and then densified under a high pressure of 4.5 GPa at 1273 K for 10 min. The method led to the densification of 8YSZ to a relative density higher than 92% without grain growth. Fourier transmission Raman spectroscopy suggested that 8YSZ underwent a phase transition from the cubic phase to a phase mixture (tetragonal plus a trace of monoclinic) after the densification, which decreased the electrical conductivity to a certain degree as concluded from the impedance spectroscopy.

Polyelectrolyte-functionalized ionic liquid for electrochemistry in supporting electrolyte-free aqueous solutions and application in amperometric flow injection analysis

As a green process, electrochemistry in aqueous solution without a supporting electrolyte has been described based on a simple polyelectrolyte-functionalized ionic liquid (PFIL)-modified electrode. The studied PFIL material combines features of ionic liquids and traditional polyelectrolytes. The ionic liquid part provides a high ionic conductivity and affinity to many different compounds. The polyelectrolyte part has a good stability in aqueous solution and a capability of being immobilized on different substrates. The electrochemical properties of such a PFIL-modified electrode assembly in a supporting electrolyte-free solution have been investigated by using an electrically neutral electroactive species, hydroquinone ( HQ) as the model compound. The partition coefficient and diffusion coefficient of HQ in the PFIL film were calculated to be 0.346 and 4.74 X 10(-6) cm(2) s(-1), respectively. Electrochemistry in PFIL is similar to electrochemistry in a solution of traditional supporting electrolytes, except that the electrochemical reaction takes place in a thin film on the surface of the electrode. PFILs are easily immobilized on solid substrates, are inexpensive and electrochemically stable. A PFIL-modified electrode assembly is successfully used in the flow analysis of HQ by amperometric detection in solution without a supporting electrolyte.

Grain boundary conductivity of high purity neodymium-doped ceria nanosystem with and without the doping of molybdenum oxide

Solid solutions of Ce1-xNdxO2-x/2 (0.05 <= x <= 0.2) and (Ce1-xNdx)(0.95)MO0.05O2-delta (0.05 <= x <= 0.2) have been synthesized by a modified sol-gel method. Both materials have very low content of SiO2 (similar to 27 ppm). Their structures and ionic conductivities were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and electrochemical impedance spectroscopy (M). The XRD patterns indicate that these materials are single phases with a cubic fluorite structure. The powders calcined at 300 degrees C with a crystal size of 5.7 nm have good sinterability, and the relative density could reach above 96% after being sintered at 1450 degrees C. With the addition Of MoO3, the sintering temperature could be decreased to 1250 degrees C. Impedance spectroscopy measurement in the temperature range of 250-800 degrees C indicates that a sharp increase of conductivity is observed when a small amount of Nd2O3 is added into ceria, of which Ce0.85Nd0.15O1.925 (15NDC) shows the highest conductivity. With the addition of a small amount Of MoO3, the grain boundary conductivity of 15NDC at 600 degrees C increases from 2.56 S m(-1) to 5.62 S m(-1).

Preparation, structure and oxide ion conductivity in Ce6-xYxMoO15-delta (x=0.1-1.4) solid solutions

The Ce6-xYxMoO15-delta solid solution with fluorite-related structure have been characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), IR, Raman, scanning electric microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The electric conductivity of samples is investigated by Ac impedance spectroscopy. An essentially pure oxide-ion conductivity of the oxygen-deficiency was observed in pure argon, oxygen and air. The highest oxygen-ion conductivity was found in Ce5.5Y0.5MoO15-delta ranging from 5.9 X 10(-5)(S cm(-1)) at 300 degrees C to 1.3 X 10(-2)(S cm(-1)) at 650 degrees C, respectively. The oxide-ion conductivities remained stable over 80 h-long test at 800 degrees C. These properties suggested that significant oxide-ionic conductivity exists in these materials at moderately elevated temperatures.

Electrochemical and bioelectrochemistry properties of room-temperature ionic liquids and carbon composite materials

Room-temperature ionic liquids (RTILs) are liquids at room temperature and represent a new class of nonaqueous but polar solvents with high ionic conductivity. The conductivity property of carbon nanotubes/RTILs and carbon microbeads/RTILs composite materials has been studied using ac impedance technology. Enzyme coated by RTILs-modified gold and glassy carbon electrodes allow efficient electron transfer between the electrode and the protein and also catalyze the reduction Of O-2 and H2O2,

A single ionic conductor based on Nafion and its electrochemical properties used as lithium polymer electrolyte

In an attempt to raise the transport number of Li+ to nearly unity in solid polymer electrolytes, commercial perfluorinated sulfonate acid membrane Nafion 117 was lithiated and codissolved with copolymer poly(vinylidene fluoride)hexafluoropropylene. The effect of fumed silica on the physical and electrochemical properties of the single ion conduction polymer electrolyte was studied with atom force microscopy, fourier transform infrared spectroscopy, differential scanning calorimetry, and electrochemical impedance spectroscopy. It was confirmed that the fumed silica has an obvious effect on the morphology of polymer electrolyte membranes and ionic conductivity. The resulting materials exhibit good film formation, solvent-maintaining capability, and dimensional stability. The lithium polymer electrolyte after gelling with a plasticizer shows a high ionic conductivity of 3.18 x 10(-4) S/cm.

Study of the conductivity and side chain mobility of a comb-like polymer electrolyte using the dynamic mechanical method

Using poly(styrene-co-maleic anhydride) as a backbone and poly(ethylene glycol) methyl ether (PEGME) with different molecular weights as side chains, three comb-like polymers and their Li salt complexes were synthesized. The dynamic mechanical properties and conductivities were investigated. Results showed that the polymer electrolytes possess two glass transitions: alpha -transition and beta -transition, and the temperature dependence of the ionic conductivity shows WLF (Williams-Landel-Ferry) behavior. Based on the time-temperature equivalence principle, a master curve was constructed by selecting T-beta as reference temperature. The values of the WLF parameters (C-1 and C-2) were obtained and were found to be almost independent of the length of the PEGME side chain and the content of Li salt. By reference to T-0 = 50 degreesC. the relation between log tau (c) and c was found to be linear. The master curves are displaced progressively to higher frequencies as the molecular weight of the side chain is increased. The relation between log tau (n) and the molecular weight of the side chain is also linear. (C) 2001 Elsevier Science B.V. All rights reserved.

Thermal, mechanical and ionic conductive behaviour of gamma-radiation induced PEO/PVDF(SIN)-LiClO4 polymer electrolyte system

An effort has been made to modify the mechanical behaviour of our previously reported gel-type gamma-radiation crosslinked polyethylene oxide (PEO)-LiClO4 polymer electrolyte. A highly polar and gamma-radiation crosslinkable crystalline polymer, polyvinylidene fluoride (PVDF), was selected to blend with PEO and then subjected to gamma-irradiation in order to make an simultaneous interpenetrating network (SIN), which was used as a polymer host to impart stiffness to the plasticized system. Experimental results have shown that the presence of PVDF in the system, through gamma-radiation induced SIN formation, could not only give a rather high mechanical modulus of 10(7) Pa at ambient temperature, but also maintain the room temperature ionic conductivity at a high level (greater than 10(-4) S/cm). DSC, DMA and conductivity measurement techniques were used to examine the effects of blending, gamma-irradiation and plasticization on the variations of glass transition and melting endotherm, on the appearance of high elastic plateau and on the temperature dependence of ionic conductivity: In addition, it was found that, in contrast with the unplasticized system, the ionic conductivity mechanism of this gel-type electrolyte seems to conform to the Arrhenius model, suggesting that, as a result of the high degree of plasticization, the polymer chains act mainly as the skeleton of the networks or polymer cages to immobilize the liquid electrolyte solution, whereas the ionic species migrate as if they were in a liquid medium. (C) 1997 Elsevier Science Ltd.

The relation between molecular motion and ion conductivity on a new comblike polymer

A new amorphous comblike polymer(CBP) based on methylvinyl ether/maleic anhydride alternating copolymer backbone and on oligooxyethylene side chain was synthesized The dynamic mechanical properties of CBP-Li salt complexes showed that there were two glass transitions. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration. The plot of Log sigma against 1/(T-To) shows an unusual dual VTF behavior when using sidechain glass transition temperature (T-beta) as To.