Increase of ionic conductivity in the microporous lithosilicate RUB-29 by Na-ion exchange processes

The ionic conductivity in the zeolite-like lithosilicate RUB-29 (Cs14Li24[Li18Si72O172]·14H2O [S.-H. Park, J.B. Parise, H. Gies, H. Liu, C.P. Grey, B.H. Toby, J. Am. Chem. Soc. 122 (2000) 11023–11024]) increases via simple ion-exchange processes, in particular when Na cations replace a part of Cs+ and Li+ of the material. The resulting ionic conductivity value of 3.2×10−3 S cm−1 at 885 K is about two orders higher than that for the original material [S.-H. Park, J.B. Parise, M.E. Franke, T. Seydel, C. Paulmann, Micropor. Mesopor. Mater., in print (doi:10.1016/j.micromeso.2007.03.040 available online since April 19, 2007)]. The structural basis of a Na+-exchanged RUB-29 sample (Na-RUB-29) at 673 K could be elucidated by means of neutron powder diffraction. Rietveld refinements confirmed the replacement of Na+ for both parts of Cs and Li cations, agreeing with idealized cell content, Na8Cs8Li40Si72O172. As a result of the incorporation of Na+ in large pores, the number of Li+ vacancies in dense Li2O-layers of the structure could increase. This can be one of the main reasons for the improved conductivity in Na-RUB-29. In addition, mobile Na cations may also contribute to the conductivity in Na-RUB-29 as continuous scattering length densities were found around the sites for Na in difference Fourier map.

Li2O-layers formed by edge- and corner-sharing LiO4- and LiO3-moieties in the zeolite-like lithosilicate RUB-29 provide optimal pathways for conducting Li+. The number of empty Li sites in this layer-like configuration could increase via ‘simple’ Na+-exchange processes, promoting fast Li motions.Figure optionsDownload as PowerPoint slide