On the dependence of ionic transport on crystal orientation in NaSICON-type solid electrolytes (original) (raw)
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Ionic conduction in the solid state
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Solid state ionic conductors are important from an industrial viewpoint. A variety of such conductors have been found. In order to understand the reasons for high ionic conductivity in these solids, there have been a number of experimental, theoretical and computational studies in the literature. We provide here a survey of these investigations with focus on what is known and elaborate on issues that still remain unresolved. Conductivity depends on a number of factors such as presence of interstitial sites, ion size, temperature, crystal structure etc. We discuss the recent results from atomistic computer simulations on the dependence of conductivity in NASICONs as a function of composition, temperature, phase change and cation among others. A new potential for modelling of NASICON structure that has been proposed is also discussed.
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Structure property function relationships provide valuable guidelines in the systematic development of advanced functional materials with tailored properties. It is demonstrated that an augmented bond valence approach can be effectively used to establish such relationships for solid electrolytes. A bond valence analysis of local structure models for disordered systems or interfaces based on reverse Monte Carlo (RMC) fits or molecular dynamics (MD) simulations yields quantitative predictions of the ion transport characteristics. As demonstrated here for a range of metaphosphate and diborate glasses, the complete description of the energy landscape for mobile ions also provides an effective tool for achieving a more detailed understanding of ion transport in glasses. The investigation of time evolutions can be included, if the bond valence analysis is based on MD trajectories. In principle, this allows quantifying the time and temperature dependence of pathway characteristics, provided that a suitable empirical force-field is available. For the example of LiPO 3 , the remaining differences between simulated and experimental structures are investigated and a compensation method is discussed. Keywords. Solid electrolytes; bond valence analysis; ion transport in glasses.
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Ion transport mechanism in lithium perchlorate (LiClO 4)-succinonitrile (SN), a prototype of plastic crystalline soft matter electrolyte is discussed in the context of solvent configurational isomerism and ion solvation. Contributions of both solvent configurational isomerism and ion solvation are reflected in the activation energy for ion conduction in 0-1 M LiClO 4-SN samples. Activation energy due to solvent configurational changes, that is, trans-gauche isomerism is observed to be a function of salt content and decreases in presence of salt (except at high salt concentrations, e.g. 1 M LiClO 4-SN). The remnant contribution to activation energy is attributed to ion-association. The X-ray diffraction of single crystals obtained using in situ cryo-crystallography confirms directly the observations of the ionic conductivity measurements. Fourier transform infrared spectroscopy and NMR line width measurements provide additional support to our proposition of ion transport in the prototype plastic crystalline electrolyte.
Structure, Conductivity, and Ionic Motion in Na 1+ x Zr 2 Si x P 3 - x O 12 : A Simulation Study
The Journal of Physical Chemistry B, 2002
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