Structural and Charge Transport Properties of Composites of Phosphate-Silicate Protonic Glass with Uranyl Hydroxy-Phosphate and Hydroxy-Arsenate Obtained by Mechano-Chemical Synthesis Undergoing Hydration Changes

Materials (Basel). 2022 Dec 27;16(1):267. doi: 10.3390/ma16010267.

Abstract

The introduction of the hydrogen economy, despite its obvious technological problems, creates a need for a significant number of niche-focused solutions, such as small-sized (10-100 W) fuel cells able to run on hydrogen of lesser purity than what is considered a standard in the case of PEMFCs. One of the solutions can be derived from the fact that an increase in the operational temperature of a cell significantly decreases its susceptibility to catalyst poisoning. Electrolytes suitable for the so-called medium temperature operational range of 120-400 °C, hence developed, are neither commercialized nor standardized. Among them, phosphate silicate protonically conductive glasses were found not only to reveal interestingly high levels of operational parameters, but also, to exhibit superior chemical and electrochemical stability over their polymeric counterparts. On the other hand, their mechanical properties, including cracking fragility, still need elaboration. Initial studies of the composite phosphate silicate glasses with uranyl-based protonic conductors, presented here, proved their value both in terms of application in fuel cell systems, and in terms of understanding the mechanism governing the charge transport mechanism in these and similar systems. It was found that whereas systems containing 10-20 wt% of the crystalline additive suffer from significant instability, materials containing 45-80 wt% (with an optimum at 60%) should be examined more thoughtfully. Moreover, the uranyl hydrogen phosphate was found to surpass its arsenate counterpart as an interesting self-healing behavior of the phase structure of the derived composite was proved.

Keywords: glassy protonic conductors; mechanochemical synthesis of composites; medium temperature fuel cell; uranyl-based layered superprotonic materials.