High Electronically Conductive Tungsten Phosphate Glass-Ceramics.

High electronically conductive tungsten phosphate glass-ceramics have been prepared by the controlled crystallization of binary 60WO3-40P2O5 glass in the temperature range from 700 to 935 °C and for 1 to 24 h. The substantial increase in the conductivity for four orders of magnitude is a result of the formation of electronically conductive W2O3(PO4)2 and WO3 phases. At low crystallization temperature the dominant W2O3(PO4)2 phase is created, whereas at 935 °C for 24 h the formation of semiconducting WO3 crystallites of an average size of 80 nm enhances the conductivity to the highest value of 1.64 × 10-4 (Ω cm)-1 at 30 °C. The course of the crystallization and its impact on this exceptionally high electronic transport of binary tungsten phosphate glass-ceramics has been discussed in detail. Since such highly electronically conductive WO3-based glass-ceramics have a great potential as cathode/anode materials in solid state batteries and as electrocatalysts in fuel cells, it is of interest to provide a novel insight into the improvement of their electrical properties.

Lithium-Ion Mobility in Quaternary Boro-Germano-Phosphate Glasses.

Effect of the structural changes, electrical conductivity, and dielectric properties on the addition of a third glass-former, GeO2, to the borophosphate glasses, 40Li2O-10B2O3-(50 - x)P2O5-xGeO2, x = 0-25 mol %, has been studied. Introduction of GeO2 causes the structural modifications in the glass network, which results in a continuous increase in electrical conductivity. Glasses with low GeO2 content, up to 10 mol %, show a rapid increase in dc conductivity as a result of the interlinkage of slightly depolymerized phosphate chains and negatively charged [GeO4](-) units, which enhances the migration of Li(+) ions. The Li(+) ions compensate these delocalized charges connecting both phosphate and germanium units, which results in reduction of both bond effectiveness and binding energy of Li(+) ions and therefore enables their hop to the next charge-compensating site. For higher GeO2 content, the dc conductivity increases slightly, tending to approach a maximum in Li(+) ion mobility caused by the incorporation of GeO2 units into phosphate network combined with conversion of GeO4 to GeO6 units. The strong cross-linkage of germanium and phosphate units creates heteroatomic P-O-Ge bonds responsible for more effectively trapped Li(+) ions. A close correspondence between dielectric and conductivity parameters at high frequencies indicates that the increase in conductivity indeed is controlled by the modification of structure as a function of GeO2 addition.

Coating of zinc ferrite particles with a conducting polymer, polyaniline.

Particles of zinc ferrite, ZnOFe2O3, were coated with polyaniline (PANI) phosphate during the in situ polymerization of aniline in an aqueous solution of phosphoric acid. The PANI-ferrite composites were characterized by FTIR spectroscopy. X-ray photoelectron spectroscopy was used to determine the degree of coating with a conducting polymer. Even a low content of PANI, 1.4 wt%, resulted in the 45% coating of the particles' surface. On the other hand, even at high PANI content, the coating of ferrite surface did not exceeded 90%. This is explained by the clustering of hydrophobic aniline oligomers at the hydrophilic ferrite surface and the consequent irregular PANI coating. The conductivity increased from 2 x 10(-9) to 6.5 S cm(-1) with increasing fraction of PANI phosphate in the composite. The percolation threshold was located at 3-4 vol% of the conducting component. In the absence of any acid, a conducting product, 1.4 x 10(-2) Scm(-1), was also obtained. As the concentration of phosphoric acid increased to 3 M, the conductivity of the composites reached 1.8 S cm(-1) at 10-14 wt% of PANI. The ferrite alone can act as an oxidant for aniline; a product having a conductivity 0.11 S cm(-1) was obtained after a one-month immersion of ferrite in an acidic solution of aniline.