ELECTRIC CONDUCTIVITY OF Li+ -DOPED PILLARED MONTMORILLONITE
Abstract
The method for obtaining solid electrolytes based on layered alumosilicates with lithium conductivity (2D-pillared nanomaterials) was proposed. The procedure of synthesis involves three basic steps: (I) the expansion of the interlayer space by the intercalation of large-size metal polyhydroxocomplexes, (II) the formation by calcination of the pillared matrix with developed pore volume and high specific surface area, and (III) the doping of nanocavities of the pillared structure by the lithium ions. It was shown that for the studied Li+ -doped pillared montmorillonite samples (PMM), intercalated by the polycations [Al13O4(OH)24(H2O)12]7+ and [Al30O8(OH)56(H2O)24]18+, the conductivity was several orders of magnitude higher than that of natural montmorillonite (MM) and is comparable with the most prominent lithium solid electrolytes, starting from temperatures above 100 °C. The magnitude σ100°C (S·сm-1) increases in the series: MM (2.33·10-7), MM-Li+ (2.99·10-6), Al13-PMM-Li+ (1.64·10-5), Al30-PMM-Li+ (3.12·10-5). An ensemble of the pillars in the interlayer space provides an accelerated diffusion of lithium ions over their surface and thus enhances electrical conductivity. For the Al13-PMM-Li+ and Al30-PMM-Li+ samples at a temperature range of about 370-420 °C thermal anomalies of conductivity were observed in contrast to the unmodified montmorillonite. According to the authors, their nature is related to the chemical and structural transformations of the pillars and the accompanying reactions with lithium ions. From this example it follows that the method of the impedance spectroscopy may provide interesting additional information on the nature of chemical transformations of the polycations through an intermediate boehmite-like modification to the form of γ-Al2O3-pillars.
Forcitation:
Butman M.F., Ovchinnikov N.L., Karasev N.S. Electric conductivity of Li+ -doped pillared montmorillonite. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 9. P. 82-91
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