Abstract
We have developed new type of superconducting-superionic conducting nanohybrids, $Ag_xI_wBi_2Sr_2Ca_{n-1}Cu_nO_y$ (n=1 and 2) by applying the chimie douce reaction to the superconducting Bi-based cuprates. These nanohybrids can be achieved by the stepwise intercalation whereby the $Ag^+$ ion is thermally diffused into the pre-intercalated iodine sublattice of $IBi_2Sr_2Ca_{n-1}Cu_nO_y$. According to the X-ray diffraction analysis, the Ag-I intercalates are found to have an unique heterostructure in which the superionic conducting Ag-I layer and the superconducting $IBi_2Sr_2Ca_{n-1}Cu_nO_y$ layer are regularly interstratified with a remarkable basal increment of ~7.3$\AA$. The systematic XAS studies demonstrate that the intercalation of Ag-I accompanies the charge transfer between host and guest, giving rise to a change in hole concentration of $CuO_2$ layer and to a slight $T_c$ change. The Ag K-edge EXAFS result reveals that the intercalated Ag-I has a $\beta$-AgI-like local structure with distorted tetrahedral symmetry, suggesting a mobile environment for the intercalated $Ag^+$ ion. In fact, from ac impedance analyses, we have found that the Ag-I intercalates possess a fast ionic conductivity ($\sigma_i=10^{-1.4}\sim 10^{-2.6}\Omega^{-1}\textrm{cm}^{-1}\;at\;270^{\circ}C$ with an uniform activation energy ($\DeltaE_a=0.22\pm 0.02$ eV). More interesting finding is that these intercalates exhibit high electronic conducting as well as ionic ones ($t_i$=0.02~0.60) due to their interstratified structure consisting of superionic conducting and superconducting layers. In this respect, these new intercalates are expected to be useful as an electrode material in various electrochemical devices.
