ABSTRACT
The characteristics of cation diffusion with many-body effects are discussed using Ag ß-alumina as an example of a superionic conductor. Polarized Raman spectra of Ag ß-alumina have been measured at room temperature. The interatomic potentials were determined by a non-linear least square fitting between the phonon eigenvalues from the Raman observations and a dynamical matrix calculation based on a rigid-ion model. The obtained potential parameters for the model crystal of Ag ß-alumina successfully reproduce the macroscopic properties with respect to the heat capacity, isothermal compressibility and self-diffusion constant. A molecular dynamics (MD) calculation has been carried out using the model crystal of Ag ß-alumina to understand the many-body effects for the fast ionic diffusion. It was found that the Ag-Ag repulsion by excess Ag defects significantly reduced the cost of the energy difference of the occupancy between the stable and metastable sites. It is possible for the system to take various configurations of the mobile ions through defects easily, and then the fast ionic diffusion will appear. On the other hand, the Ag-Ag repulsion changes the dynamics of the Ag ions from a random hopping to a cooperative motion. In the cooperative motion, the ionic transport becomes difficult due to the additional energy required for the structural relaxation of the surrounding Ag ions. We propose a new insight into the superionic conduction, that is, the activation energy for the ionic transport is composed of two kinds of elements: a 'static' activation energy and a 'dynamic' one. The static activation energy is the cost of the averaged energy difference in the various structural configurations in the equilibrium state. The dynamic activation energy is the additional energy required for the structural relaxation induced by the jump process.
ABSTRACT
The polymer electrolytes composed of poly(vinyl acetate) (PVAc) with various stoichiometric ratios of lithium perchlorate (LiClO(4)) salt have been prepared by solution casting method. The techniques Fourier transform infra-red (FTIR) and Laser Raman spectroscopy have been used to monitor polymer-salt complex formation, ion-ion and ion-polymer interactions as a function of salt concentration. Significant changes in both Laser Raman and FTIR spectra are observed which reveals an interaction between ester oxygens with lithium cation coordination. These results strongly suggest the interaction of lithium cation and network polymer chains. When the salt content is increased, the intensity of the internal Raman modes of the ClO(4)(-) increases. The ClO(4)(-) stretching mode observed at 934 cm(-1) in Laser Raman shows some additional shoulder peaks with increase in salt concentration. This reveals the presence of free anions, ion contact pairs and higher order ionic clusters. From the FTIR and Laser Raman results the transport mechanism of ions in PVAc:LiClO(4) polymer electrolytes has been discussed.
Subject(s)
Lithium Compounds/chemistry , Lithium/metabolism , Perchlorates/chemistry , Polyvinyls/chemistry , Spectrum Analysis, Raman/methods , Electrolytes/chemistry , Ion Transport/physiology , Lithium Compounds/metabolism , Perchlorates/metabolism , Polymers/chemistry , Polyvinyls/metabolism , Spectroscopy, Fourier Transform InfraredABSTRACT
XAFS (X-ray absorption fine-structure) spectra were measured near K-absorption edges of Ce (40.5 keV), Dy (53.8 keV), Ta (67.4 keV) and Pt (78.4 keV). The blunt K-edge jump due to the finite lifetime of the core hole was observed. This makes it difficult to extract EXAFS (extended X-ray absorption fine-structure) functions at low k values. Local structure parameters can be evaluated from the EXAFS spectra above K-absorption edges in the high-energy region as well as from those above L(III)-edges. It was found that the finite-lifetime effect of the core hole is effectively taken into the photoelectron mean-free-path term, as predicted theoretically.
