Monte Carlo simulation of diffusion and ionic conductivity in a simple cubic random alloy via the interstitialcy mechanism.

This Monte Carlo study deals with mass and charge transport in binary ionic alloys governed by interstitialcy defects acting as diffusion vehicles. In particular, we calculate tracer correlation factors f(A) and f(B) in a simple cubic random alloy AB for diffusion via the collinear interstitialcy mechanism as a function of composition and jump frequency ratio wA/wB. [corrected]. Interstitialcy correlation factors f(I), which play a crucial role in the interpretation of ion-conductivity data, are also determined. The evaluation of partial correlation factors provides insight into the types of jumps that mostly contribute to the different transport processes under consideration. Examination of the percolation behaviour yields the site-percolation threshold of the mobile component B for w(A) = 0. Surprisingly, a unique second-order threshold composition is found, which relates to the abundance of different interstitialcy jump types when wA << wB [corrected]. Both numerically obtained threshold values are accurately reproduced by estimated analytical expressions based on simple arguments. Practical implications of the simulation results are explored by calculating tracer diffusivity ratios D*(A)/D*(B) and by comparing self-diffusion with ionic conductivity using the Nernst-Einstein equation.

Foreign-ion and self-ion diffusion in a crosslinked salt-in-polyether electrolyte.

We present an extensive study of ionic transport in PolyG(30)LiPF(6), which is a crosslinked poly(ethylene oxide)-poly(propylene oxide(PEO-PPO) random copolymer complexed with LiPF(6) to an oxygen-to-cation ratio of 30 : 1. Self-diffusion coefficients of the constituent ions were measured by pulsed field gradient nuclear magnetic resonance (PFG-NMR) as a function of temperature using the signals of (7)Li and (19)F. These data were compared with the charge diffusivity as derived with the Nernst-Einstein equation from the ion conductivity obtained by impedance spectroscopy. In addition, the diffusion behaviour of a foreign cation (sodium) and that of a foreign anion (iodine) in PolyG(30)LiPF(6) were investigated by means of the radiotracers (22)Na and (125)I. All different types of diffusivities were evaluated in a comprehensive ion transport model which allows for the occurrence of charged single ions and neutral ion pairs. Simultaneous fitting of all data within this model yields best values of the model parameters which include Vogel-Tammann-Fulcher parameters and enthalpies/entropies of pair formation. Two distinct variants of the same general model reproduce the experimental data equally well, i.e., with closely similar results for the pair contribution to the migration of each ionic species. In the first variant, this pair contribution is due to a small fraction of ion pairs with a high mobility. By contrast, the second variant results in a very large fraction of pairs characterized by a relatively low mobility. The assumptions and implications connected with both model variants are discussed in detail.

Mass and charge transport in the PEO-NaI polymer electrolyte system: effects of temperature and salt concentration.

Ionic transport in amorphous complexes of poly(ethylene oxide) (PEO) and sodium iodide (NaI) was investigated by means of radiotracer diffusion and electrical conductivity measurements for three different compositions characterised by O-to-Na ratios of 20, 30, and 60. The diffusivity of 22Na and 125I as well as the charge diffusivity each show a systematic dependence on both temperature and salt concentration. The experimental data can be described within a transport model based on the occurrence of neutral ion pairs in addition to charged single cations and anions. It is found that both the enthalpy and entropy of ion pair formation decrease with increasing salt concentration. This indicates that the state of coordination between cations and polymer chain segments correlates with the number of available oxygen atoms per cation.

Radiotracer diffusion and ionic conduction in a PEO-NaI polymer electrolyte.

We studied ion transport in amorphous PEO30NaI consisting of poly(ethylene oxide) and sodium iodide in a Na-to-O ratio of 30. Diffusion coefficients of the radiotracers 22Na and 125I were measured for temperatures between 67 and 180 degrees C and compared with the overall charge diffusivity deduced from dc conductivity data. To explain the observed discrepancy between the sum of the tracer diffusivities and the charge diffusivity we propose a detailed model which is based on the formation of neutral ion pairs. Evaluating simultaneously all experimental data within this model yields not only the true diffusion coefficient of all individual species but also the ion-pairing reaction constant as a function of temperature.