Charge transfer in mixed proton, oxygen ion and electron solid oxide conductor

Analysis of the equivalent scheme of the mixed proton-oxygen ion-electron conductor (MPOEC) allowed to obtain relationships between parameters of the membrane (total conductivity and transfer numbers) and parameters of the charge and mass transfer through the membrane (partial ion and electron currents, the specific flux of hydrogen at the cathode membrane surface) under regime of electrochemical reforming. It was stated that presence of proton conductivity in addition to oxygen ion conductivity led to increase of total flux of produced hydrogen. However, under conditions typical for the electrochemical reforming of methane into hydrogen, the specific hydrogen flux is about four times lower in the case when the membrane has proton-electron conductivity than in the case when the membrane has oxygen ion-electron conductivity. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Solid vitreous electrolytes based on the system Li2O-Li2SO4-B2O3-MoO3 for rechargeable lithium power sources

In the given work with the purpose of improvement of moistening ability of sulfoborate solid vitreous electrolyte (SVE) in their structure entered molybdenum oxide (VI). Reduction of wetting angle, i.e. improvement of electrode wetting by a SVE-melt, accompanied by better electrode (aluminium) /SVE interface contact formation. Accordingly, the interface impedance is reduced. As a result of the carried out experiments is established, that the modifying SVE by molybdenum oxide (VI) renders complex positive influence on its physical-chemical properties, namely: improves X-ray-amorphism, raises ionic conductivity, reduces electronic conductivity and effective energy of ion conductivity activation. At comparison of properties modified SVE and "LiPON", it is visible, that the ratio between ionic and electronic conductivity for modified SVE approximately on the order is higher, than for "LiPON". Ionic conductivity of the modified SVE higher than conductivity of "LiPON". The low value of electronic conductivity investigated SVE on a background ionic is the positive factor from the point of view of their use in lithium power sources. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Organic-inorganic nanocomposite materials prepared by the sol-gel route as new ionic conductors in quasi solid state electrolytes

Nanocomposite organic/inorganic materials made through sol-gel method exhibit high values of ionic conductivity when they were impregnated with the redox couple I ₃ ⁻ /I⁻ Two different kinds of nanocomposite materials, depending on the different interactions between silica and poly(ethylene)oxide or poly(propylene)oxide blends, were prepared by the sol-gel technique in room temperature. Gels, for both nanocomposite materials, were obtained by acetic acid catalyzed solvolysis and were regulated by formation of intermediate products, such as silicon ester and -Si-O-Si-oligomers. Time-resolved fluorescence techniques and conductivity measurements were performed in order to define the parameters which allow maximum probe mobility and minimum confinement conditions with the aim to apply these materials in quasi solid state electrolytes. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

The nature of conduction pathways in mixed alkali phosphate glasses

In this paper we discuss the nature of the ion conduction pathways in Li_xRb_1−xPO₃ glasses. Our investigations are based on a bond valence analysis of reverse Monte Carlo (RMC) produced structural models in quantitative agreement with neutron and X-ray diffraction data. In a previous letter [11] we have shown that this approach enables us to reproduce and understand the mixed alkali effect (MAE) directly from the structural models. The results have shown that the drastic drop of the conductivity for an intermediate composition (x ≈ 0.5) is mainly caused due to the blocking by immobile unlike cations, which is highly effective since the two types of alkali ions are randomly mixed and have distinctly different conduction pathways of low dimensionality. Here, we explore the local dimensionality of the pathways and discuss its implications for the network of pathways and the related ionic conductivity. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

D.C. conductivity of transparent conductive ZnO:Al films in the temperature range 80–360 K

An experimental study of the temperature dependence of the d.c. conductivity σ as a function of temperature T in the range from 80–360 K on nanocrystalline ZnO:Al films (Al³⁺ 2%) of thickness 500 nm prepared on glass microscope slides by a dip — coating method is presented. The electrical conductivity σ, which at room temperature varied between 0.1 to 2.7 S/cm, increased almost linearly with T for all the samples. Measurements of the Hall coefficient at room temperature and in a magnetic field of 1.2 T, gave R_H=0.53 cm³C⁻¹, from which a carrier concentration of n=1.18×10¹⁹ cm⁻³ and a carrier mobility of μ=1.40 cm²/Vs were deduced. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

Two-dimensional NMR relaxation study of the pore structure in silicone hydrogel contact lenses

A combination of two-dimensional nuclear magnetic resonance (NMR) proton relaxometry and differential interference contrast optical microscopy is used to compare the pore structures of hydroxyethyl methacrylate-based hydrogels used in conventional contact lenses with three silicone hydrogels primarily developed for continuous-wear contact lenses. It is shown that both types of hydrogel have a connected network of nanopores but that, in addition, the silicone hydrogels contain pores on the micrometer scale that enhances their permeability. The potential of other two-dimensional NMR relaxation and diffusion methods for detailed characterization of hydrogels is discussed.     

Quantitative and high mass ToF-SIMS studies of siloxane segregation in hydrogel polymers using cryogenic sample handling techniques

This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%.     

Synthesis and electrical characterisation of the apatite-type oxide ion conductors Nd9.33+xSi6-yGayO26+z

Apatite-type oxides have been attracting interest as a new class of oxide ion conductors. In this paper we examine the effect of Ga doping on the conductivity of the apatite silicate system, Nd_9.33+xSi₆O_26+3x/2 and compare the results to those reported for similar doping studies in La_9.33+xSi₆O_26+3x/2. The highest conductivities are observed for samples containing oxygen excess, which is in agreement with previous reports that interstitial oxide ions are important for high oxide ion conduction in these materials. For oxygen stoichiometric materials, i.e. Nd_9.33+x/3Si_6-xGa_xO₂₆, the Ga doping results in a significant increase in activation energy and a consequent lowering of the low temperature conductivity. This is contrary to results previously reported for the La containing analogues, which showed an enhancement of conductivity on Ga doping up to x=1.5. Possible explanations for the differences between the two systems are discussed. Paper presented at the Patras Conference on Solid State Ionics — Transport Properites, Patras, Greece, Sept. 14 – 18, 2004.     

Electronic structure and covalency in superionic conductors

The electronic states of noble metal halides and alkali halides are calculated by the DVXα cluster method to get more microscopic evidence for the p — d hybridization and the covalency in noble metal halides. It is found that both components of anti-bonding and bonding exist in the diagram of overlap population (DOP) for AgX (X=halogen) and these two components are made up of the 4d band of Ag ion and the p band of halogen ion, which form the p — d hybridization. The covalency of noble metal halides is in the border between that of the fourfold coordinated compounds such as AgI and that of the sixfold coordinated compounds such as AgCl. These calculation results on the covalency are compared with the Phillips's ionicity. Paper presented at the Patras Conference on Solid State Ionics, Patras, Greece, Sept. 14 – 18, 2004.     

Novel trivalent cation conducting solids and their application

Among the trivalent ion conductors reported, the highest ion conductivity was realized with the trivalent Al³⁺ ion conducting (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte and the value enters into the region between yttria stabilized zirconia (YSZ) and calcia stabilized zirconia (CSZ) that are well known to be high oxide anion conductors commercialized. The improvement of the ion conductivity and the mechanical strength was simultaneously achieved by adding B₂O₃ during the sintering procedure. The Al³⁺ ion conducting (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid electrolyte with B₂O₃ treatment was combined with YSZ, and the 0.7La₂O₂SO₄-0.3Li₂SO₄ solid was attached on the (Al_xZr_1−x)_4/(4−x)Nb(PO₄)₃ solid surface as the auxiliary electrode for sulfur dioxide (SO₂) gas sensing. The sensor response was rapid, reproducible and continuous with obeying the Nernst theoretical relationship. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Development of oxygen ion conductors: One relevant tendency

In the past ten years a series of developments in the field of materials with dominant oxygen ion conduction introduced a variety of new systems. The most relevant aspect is a shift from ionic transport mechanisms based on the motion of oxygen vacancies, to mechanisms based on mobile oxygen interstitials. In parallel, structures identified with dominant oxygen ion conduction moved from the relatively simple fluorite related ones to more complex materials, namely with the apatite-type and related structures, including coexistence of ionic and covalent bonding. This shift is understood as a major development, opening a wide range of alternative solutions for further exploitation. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Anode materials for lithium ion batteries in the Li-Zn-P system

This paper presents an exhaustive study of the Li-Zn-P system through the synthesis and electrochemical characterisation of several binary and ternary phases: Li₉ZnP₄, LiZnP, Zn₃P₂ (α and β), ZnP₂ (α and β), LiZn, and LiZn₄. Three synthetic routes have been used to prepare these materials: ceramic synthesis and ball milling without and with annealing. Li-Zn-P system phases have been evaluated through X-ray diffraction and electrochemical reactivity towards lithium. Exhibiting high specific capacities at potentials close to 0.7 V vs. Li⁺/Li, some of these materials are promising as negative electrode materials for lithium ion battery. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Ionic conduction and chemical bonds of Li ion in La4/3−yLi3yTi2O6

The electronic state of La_4/3−yLi_3yTi₂O₆ (y=0.21) was studied by the DV-Xα cluster method. Four model clusters were used to calculate the density of state (DOS), the bond overlap population (BOP) and the net charge (NC). A Li ion in the model cluster was moved from 1b site to another 1b site along the x axis, and the BOP and the NC calculated were discussed. Furthermore, we calculated the potential energy with the movement of the Li ion along the x axis. Paper presented at the Patras Conference on Solid State Ionics - Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Polymer electrolytes plasticized with hyperbranched polymer for lithium polymer batteries

Hyperbranched polymers (HBPs) with different terminal groups and different ethylene oxide (EO) chain lengths were prepared, and the influence of the HBP structures including molecular weights and molecular weight distribution on the ionic conductivity and the mechanical property of the composite polymer electrolytes composed of poly (ethylene oxide) (PEO), HBP, BaTiO₃ as a ceramic filler, and LiN(CF₃SO₂)₂ as a lithium salt were investigated. It was found that the molecular weights of the HBP do not affect significantly the ionic conductivity, but the molecular weight distribution might affect it, and also further branching at the terminals of the HBP led to a decrease in the ionic conductivity. The HBP with longer EO chain length was effective for enhancement of the ionic conductivity in comparison with the HBP with shorter one. The increase in cross-linkable groups (acryloyl group) at the terminals of the HBP improved the tensile strength, but caused the ionic conductivity to decrease. Loosely cross-linked composite polymer electrolyte showed higher ionic conductivity and higher tensile strength than no cross-linked one. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Effect of biotite content of hydrogels on enhanced removal of methylene blue from aqueous solution

A series of chitosan-g-poly(acrylic acid)/biotite (CTS-g-PAA/BT) hydrogels with unique clay biotite (BT) were prepared and used to remove cationic dye methylene blue (MB) from aqueous solution by batch adsorption experiments. Variables of the system including BT content, initial pH, contact time, initial concentration, and temperature affecting the adsorption efficiency of MB by CTS-g-PAA/BT hydrogels were investigated. Kinetic studies indicated that the adsorption data well followed pseudo-second-order kinetics. Langmuir and Freundlich isotherm models were applied to experimental equilibrium data of MB adsorption depending on temperature. The adsorption equilibrium data obeyed Langmuir isotherm, and the monolayer adsorption capacity calculated from the Langmuir isotherm was 2,125.70 mg/g for CTS-g-PAA/10% BT at 30 °C. The adsorption capacity was much higher compared with other hydrogels with the same content of other clays. The introduction of BT into the hydrogel could effectively improve its adsorption properties and reduce the cost. Thermodynamic parameters were evaluated for the dye-adsorbent systems and revealed that the adsorption process was spontaneous and exothermic in nature. All the information gave an indication that CTS-g-PAA/10% BT could potentially be applied as an efficient adsorbent for cationic dye removal from aqueous solution.     

Analysis of lithium and hydrogen movement in functional solid materials by neutron radiography

The principle and availability of Neutron Radiography are demonstrated. The technique is actually applied to obtain the images as to lithium in the oxide lithium ion conductors and/or hydrogen in the hydrogen storage alloys. From analysis of the lithium or hydrogen distribution, the ionic transport number and the diffusion coefficient can be calculated and the hydrogenation process is discussed. In the case imaging the special cross-section in the sample, Neutron Computed Tomography is more favorable. Here, it will be demonstrated using our actual experimental results that the NCT technique is also useful in the field of Solid State Ionics to clarify the ion distribution and movement. Paper presented at the Patras Conference on Solid State Ionics, Patras, Greece, Sept. 14–18, 2004.     

Rheological properties and impedance spectroscopy of PMMA-PVdF blend and PMMA gel polymer electrolytes for advanced lithium batteries

In the present study, blend ionic conducting membranes formed by poly(methylmethacrylate (PMMA) / poly(vinilydenefluoride) (PVDF) (blend ratio PMMA/PVdF=80/20), lithium perchlorate (LiClO₄) as a salt and a mixture of ethylene carbonate (EC)-propylene carbonate (PC) as plasticizer are prepared and characterized by impedance spectroscopy and dynamic rheological experiments. We compared the results obtained on the blends with those on PMMA gel-based polymer electrolytes incorporating the same EC/PC mixture of plasticizer and the same quantities of salt. The main focus of this study is to illustrate the rheological data of the gels and blends electrolytes to point up their mechanical stability with the temperature in sight of the technological application. The conductivity values are reported in the 20–100 °C temperature range for different lithium salt contents, while the rheological behaviour has been recorded up to 140 °C. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Sodium superionic conductor sputter-deposited coatings

Thin sodium superionic conductor (Nasicon) coatings are deposited on rotating substrates by co-sputtering in the reactive mode of a Zr-Si and a Na₃PO₄ target. The influence of the discharge current and of the target-to-substrate distance is investigated owing to the targeted Na₃Zr₂Si₂PO₁₂ stoichiometry. A thermo-structural analysis shows that the amorphous as-deposited coating of convenient composition crystallises around 700 °C in the monoclinic structure. Electrical measurements performed at room temperature after various annealing treatments indicate a ionic conductivity of about 2·10⁻³ S·cm⁻¹, consistent with that of bulk Nasicon. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Electrical properties of TiO<Subscript>2</Subscript>: equilibrium vs dynamic electrical conductivity

The present work reports semiconducting properties of high purity TiO₂ determined in the gas/solid equilibrium, as well as during controlled heating and cooling in the range 300–1,273 K. The activation energy of the electrical conductivity is considered in terms of the activation enthalpy of the formation of ionic defects and the activation enthalpy of the mobility of electronic defects. These data, determined from the dynamic electrical conductivity experiments, are compared to the electrical conductivity data determined in equilibrium. It is shown that only the equilibrium electrical conductivity data for high-purity TiO₂ are well defined. It is shown that the activation energy of the electrical conductivity determined in equilibrium differs substantially from that for the dynamic electrical conductivity data during cooling and heating. It is concluded that the formation enthalpy term determined from the dynamic conductivity data is determined by the heating/cooling rate rather than materials’ properties.     

Interface design in nanosystems of Advanced Superionic Conductors

First attempt of practical realization of new interface engineering approach “from advanced materials to advanced devices” for nanosystems of Advanced Superionic Conductors (ASICs), based on AgI (CuI) compounds is presented. Crystallochemical method of symmetry perfect ASIC//electrode interface searching is developed. Some new theoretical results of ASIC//indifferent electrode conjugated commensurate heteropairs with coherent interfaces and preliminary experimental results of the creation of thin-film supercapacitor — prototype based on the lattice matched heterojunction — are given. Future perspectives of the ASIC//electrode interface design suited for micro(nano)electronics and microsystem technology (MST) are discussed. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.