Using pressure, temperature and frequency as variables to study the dynamics of mobile ions in materials with disordered structures
Institut für Physikalische Chemie und SFB 458, Westfälische Wilhelms-Universität, Corrensstraße 30, 48149 Münster, Germany
2 NRW Graduate School of Chemistry, Westfälische Wilhelms-Universität, Corrensstraße 30, 48149 Münster, Germany
3 University of Aberdeen, Department of Chemistry, Meston Walk, Aberdeen, UK
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Complementary ways for studying the motion of mobile ions in materials with disordered structures are obtained by varying pressure, tempe- rature and frequency. New results are presented based on a combination of experimental work and modelling. Pressure-dependent measurements on alkali borate glasses show there is a remarkable difference between the activation volumes for conduction and diffusion, with ΔVσ< ΔVD, implying that the Haven ratio decreases with increasing pressure. We propose a mechanism that is characterised by a directionally positive correlation between successive hops of different ions into a moving vacant site. The effect of increasing pressure is to increase the degree of directional correlation and thus to make the conduction pathways increasingly linear in aspect. In sodium borate glasses with much lower sodium content, a maximum has been observed when ionic conductivity is plotted versus temperature at fixed frequency. This feature is identified as being of the nearly constant loss (NCL) type, caused by localised flip-flop movements of interacting charges in the B2O3 network. In crystalline γ-RbAg4I5, a related localised effect has also been found, in this case caused by activated hops of silver ions confined within structural “pockets”. Finally, the frequency dependence of the ionic conductivity is reviewed in fragile ionic melts. Fragility is interpreted here as a consequence of the shape of the local ionic potentials, which unlike in glass do not reflect the pre-existence of empty cation sites for successive ions to hop into. This difference in short-range, short-time behaviour leads directly to the emergence of non-Arrhenius dc conductivity and fluidity behaviours in molten salts. We are thus able to establish a common phenomenological and theoretical approach to ion transport in a wide range of systems, largely based on broadband conductivity spectroscopy.
© EDP Sciences, Springer-Verlag, 2008