Abstract: In 2014, present-day scientists had the opportunity of marking the centennial of a discovery that triggered the development of a new field of research, which is now called Solid State Ionics.In their 1914 paper, Carl Tubandt and Erich Lorenz reported on the extraordinary properties of the alpha phase of silver iodide. Although α-AgI was a crystalline material, it resembled a molten salt with regard to the liquid-like value and weak temperature dependence of its ionic conductivity. With their transference measurements, Tubandt and Lorenz proved that the electric current in α-AgI was completely carried by the silver ions, while the iodide ions formed a rigid lattice. Up to the present day, α-AgI has been considered the fast ion conductor par excellence.In the mid-1930s, L.W. Strock was the first to use x-ray diffraction to investigate the crystal structure of α-AgI. The anion sublattice was found to be body centered cubic, but the arrangement of the silver ions remained a puzzling question. On the one hand, Strock could assign a large number of possible crystallographic sites to them. On the other hand, the state of the silver ions appeared to be rather ‘quasi-molten’ or ‘liquid-like’. This structural puzzle was resolved in 1977, when Cava, Reidinger and Wuensch used the results of a single-crystal neutron-diffraction experiment to construct contour plots for the probability density of the silver ions in α-AgI, which turned out to have broad maxima at the tetrahedral voids of the anion structure, with saddle points between them.A number of novel experimental approaches toward a better understanding of the ion dynamics in α-AgI were suggested by Wilhelm Jost in the 1960s and 1970s. These included high-accuracy specific heat measurements, measurements of the ionic conductivity in the microwave and far-infrared frequency regimes, and quasielastic neutron scattering. The results of the ensuing experiments, involving the present author, did not always provide immediate answers to the long-standing open questions, but rather created new puzzles instead. In this Chapter, an overview is given of the essential steps that were taken in experiment and modeling, eventually leading to the emergence of a self-consistent picture of the structure and dynamics of the mobile silver ions in α-AgI. Notably, that picture included both solid-like and liquid-like aspects. Strictly speaking, however, either category, ‘solid’ and ‘liquid’, had to be considered inappropriate for characterizing the actual state of the silver-ion sublattice.Recently, the transition to a more solid-like behavior of the mobile silver ions was observed in low-temperature α-AgI, which could be stabilized by confinement in glass, as first shown by Tatsumisago et al. Far below the regular phase transition temperature, 147 °C, measurements were performed of the frequency-dependent conductivity of α-AgI, yielding relevant information on the silver-ion dynamics. A conjecture put forward by Jost in 1937 could thus be corroborated by the present author and his coworkers. Below 147 °C, the ‘liquid-like’ activation energy for ionic transport was found to be replaced by a larger, more ‘solid-like’ value, although the anion structure and, therefore, the barriers for elementary displacements of the cations remained essentially unchanged. The underlying mechanism is sketched at the end of the Chapter.
Abstract: In this chapter, we review the Nernst-Planck equation describing the cation interdiffusion coefficient, the two tracer cation diffusion coefficients and the thermodynamic factor in ionic compounds and how it is related to the analogous Darken-Manning relationship in binary alloy systems. We make use of the Onsager flux equations of non-equilibrium thermodynamics to rigorously address the problem. The recently found correction factor to the Nernst-Planck equation is analyzed visually by means of computer simulation
Abstract: In this Chapter we review knowledge about diffusion and cation conduction in oxide glasses. We first remind the reader in Section 1 of major aspects of the glassy state and recall in Section 2 the more common glass families. The diffusive motion in ion-conducting oxide glasses can be studied by several techniques – measurements of radiotracer diffusion, studies of the ionic conductivity by impedance spectroscopy, viscosity studies and pressure dependent studies of tracer diffusion and ion conduction. These methods are briefly reviewed in Section 3. Radiotracer diffusion is element-specific, whereas ionic conduction is not. A comparison of both types of experiments can throw considerable light on the question which type of ions are carriers of ionic conduction. For ionic conductors Haven ratios can be obtained from the tracer diffusivity and the ionic conductivity for those ions which dominate the conductivity.In the following sections we review the diffusive motion of cations in soda-lime silicate glass and in several alkali-oxide glasses based mainly on results from our laboratory published in detail elsewhere, but we also take into account literature data.Section 4 is devoted to two soda-lime silicate glasses, materials which are commonly used for window glass and glass containers. A comparison between ionic conductivity and tracer diffusion of Na and Ca isotopes, using the Nernst-Einstein relation to deduce charge diffusivities, reveals that sodium ions are the carriers of ionic conduction in soda-lime glasses. A comparison with viscosity data on the basis of the Stokes-Einstein relation shows that the SiO2 network is many orders of magnitude less mobile than the relatively fast diffusing modifier cations Na. The Ca ions are less mobile than the Na ions but nevertheless Ca is considerably more mobile than the network.Section 5 summarizes results of ion conduction and tracer diffusion for single Na and single Rb borate glasses. Tracer diffusion and ionic conduction have been studied in single alkali-borate glasses as functions of temperature and pressure. The smaller ion is the faster diffusing species in its own glass. This is a common feature of all alkali oxide glasses. The Haven ratio of Na in Na borate glass is temperature independent whereas the Haven ratio of Rb diffusion in Rb borate glass decreases with decreasing temperature.Section 6 reviews major facts of alkali-oxide glasses with two different alkali ions. Such glasses reveal the so-called mixed-alkali effect. Its major feature is a deep minimum of the conductivity near some middle composition for the ratio of the two alkali ions. Tracer diffusion shows a crossover of the two tracer diffusivities as functions of the relative alkali content near the conductivity minimum. The values of the tracer diffusivities also reveal in which composition range which ions dominate ionic conduction. Tracer diffusion is faster for those alkali ions which dominate the composition of the mixed glass.Section 7 considers the pressure dependence of tracer diffusion and ionic conduction. Activation volumes of tracer diffusion and of charge diffusion are reviewed. By comparison of tracer and charge diffusion the so-called Haven ratios are obtained as functions of temperature, pressure and composition. The Haven ratio of Rb in Rb borate glass decreases with temperature and pressure whereas that of Na in Na borate glass is almost constant.Section 8 summarizes additional common features of alkali-oxide glasses. Activation enthalpies of charge diffusion decrease with decreasing average ion-ion distance. The Haven ratio is unity for large ion-ion distances and decreases with increasing alkali content and hence with decreasing ion-ion distance.Conclusions about the mechanism of diffusion are discussed in Section 9. The Haven ratio near unity at low alkali concentrations can be attributed to interstitial-like diffusion similar to interstitial diffusion in crystals. At higher alkali contents collective, chain-like motions of several ions prevail and lead to a decrease of the Haven ratio. The tracer diffusivities have a pressure dependence which is stronger than that of ionic conductivity. This entails a pressure-dependent Haven ratio, which can be attributed to an increasing degree of collectivity of the ionic jump process with increasing pressure. Monte Carlo simulations showed that the number of ions which participate in collective jump events increases with increasing ion content – i.e. with decreasing average ion-ion distance. For the highest alkali contents up to four ions can be involved in collective motion. Common aspects of the motion process of ions in glasses and of atoms in glassy metals are pointed out. Diffusion in glassy metals also occurs by collective motion of several atoms.Section 10 summarizes the major features of ionic conduction and tracer diffusion and its temperature and pressure dependence of oxide glasses.
Abstract: The recently developed bombardment induced ion transport (BIIT) technique is reviewed. BIIT is based on shining an energy-selected alkali ion beam at the surface of a sample of interest. Attachment of these ions leads to the build-up of a surface potential and a surface particle density. This in turn generates the corresponding gradients which induce ion transport towards a single metal electrode connected to the backside of the sample where it is detected as a neutralization current. Two different versions of BIIT are presented, i.) the native ion BIIT and ii.) the foreign ion BIIT. The former is demonstrated to provide access to absolute ionic conductivities and activation energies, the latter leads to the generation of electrodiffusion profiles. Theoretical modelling of these concentration profiles by means of the Nernst-Planck-Poisson theory allows to deduce the concentration dependence of diffusion coefficients.
Abstract: Glassy solid electrolytes are important integral components for all-solid-state devices for energy storage and conversion. The use of multiple network formers is an important part of their design strategy for specific applications. In many glass systems the interaction between the different network formers results in strongly non-linear variations in physical properties (network former mixing (NFM) effects), requiring a detailed understanding on a structural basis.The issues to be addressed involve both the structural organization and connectivities within the framework, the local environments and spatial distributions of the mobile ions, and the dynamical aspects of ion transport, to be discussed in relation to possible phase separation or nano-segregation effects. Besides Raman and X-ray photoelectron spectroscopies, solid state nuclear magnetic resonance (NMR) methods are particularly useful for providing detailed answers to such issues. The present review introduces the basic principles of modern solid state NMR methods and their applications to glass structure, with a particular focus on the characterization of network-former mixing effects in the most common lithium and sodium conducting oxide and chalcogenide glass systems. Based on the current state of the literature reviewed in the present work, some emerging general principles governing structure/property correlations are identified, to be tested by further experimenteation in the future.