• Journal of the Korean Ceramic Society
• /
• v.33 no.6
• /
• pp.645-652
• /
• 1996

The ionic conductivity of NASICON (Na Super Ionic Conductor) solid electrolyte was simulated by using Monte Carlo Method (MCM)based on a hopping model. We assumed that the conduction path of Na ions is Na1→mid-Na→Na2 where the mid-Na sites are shallow potential sites to induce 'a breathing-like movement' of Na ions in the NASICON framework. The minimum of charge correlation factor Fc and the maximum of appeared at nearby x=2.0 The occupancy of mid-Na site affected the depth of potential barrier and the conduc-tivity of the NASICON. At above x=0.3 ln σT vs. 1/T* plots have been shown Arrhenius behavior but in (VWfc)vs. 1/T* have been shown the Arrhenius type tendency at x=1 MCM results accorded with the experi-mental procedure. The role of mid-Na on Na+ ion conduction could be explained by an additional driving force and a breating-like movement model for motions of Na+ ions in the NASICON framework. As we couldn't clearly remarked the model which is the better it seems reasonable to conclude that these hypothesies are suitable to explain the FIC behavior at NASICON.

• Journal of the Korean Ceramic Society
• /
• v.32 no.8
• /
• pp.957-965
• /
• 1995

The ionic conductivityof NASICON solid electrolytes was simulated by using Monte Carlo Method (MCM) based on a hopping model as functions of temoperature and composition. Two conduction paths were used : jumping from Na1 to Na2 and jumping from Na1 to Na2 and jumping from Na2 to Na2. Vacancy availability factor, V was affected by composition, temperature and the conduction paths. For β"-Alumina, it was known that the minimum of charge correlation factor, fc appears at the composition, p=0.5, but there was not shown the minimum of fc for NASICON. When the NASICON composition, x, approaches 2.5, the curve of In σT vs. 1/T* was shown Arrhenius behavior and also In (VWfc) was a linear function of 1/T*. The results of simulations on the considered conduction paths didn't agree with the experimental results. Thus it will be necessary to include the another Na sites as mid-Na site on the conduction path to obtain the better results.

• Journal of the Korean Ceramic Society
• /
• v.32 no.11
• /
• pp.1292-1300
• /
• 1995

The ionic conductivity of NASICON solid electrolytes was simulated by using Monte Carlo Method (MCM). There were included two conduction paths: (1) Na1-Na2 and (2) Na1-Na2 including Na2-Na2. We assumed that mid-Na ions provde an additional driving force for Na mobile ions due to the interionic repulsion between Na1 and Na2 ions. The inflection point of vacancy availability factor, V has been shown at nearby x=2, the maximum mid-Na ions. The inflection point of vacancy availability factor, V has been shown at nearby x=2, the maximum mid-Na sites are occupied. The effective jump frequency factor, V has been shown at nearby x=2, the maximum mid-Na sites are occupied. The effective jump frequency factor, W increased rapidly with the composition at low temperature, but decreased at high temperature region. On Na1-Na2 conduction path, the minimum of charge correlation factor, fc and the maximum of $\sigma$T were appeared at x=2.0. this indicated that mid-Na ions affect on the high ionic conductivity behavior. At the whole range of NASICON composition, 1n $\sigma$T vs. 1/T* plots have been shown Arrhenius behavior but 1n (VWFc) vs. 1/T* have been shown the Arrhenius type tendency at x=2, which mid-Na is being the maximum. The results of MCM agreed with the experimental one when the chosen saddle point value was 6$\varepsilon$ : 3$\varepsilon$. Here the calculated characteristic parameter of materials, K and the phase transition temperature were -4.001$\times$103 and 178$^{\circ}C$ (1/T*=1.92, 1000/T=2.22), respectively.