Protonic ceramic fuel cells (PCFCs) are promising electrochemical devices for the efficient and clean conversion of hydrogen and low hydrocarbons into electrical energy. Their intermediate operation temperature (500–800 °C) proffers advantages in terms of greater component compatibility, unnecessity of expensive noble metals for the electrocatalyst, and no dilution of the fuel electrode due to water formation. Nevertheless, the lower operating temperature, in comparison to classic solid oxide fuel cells, places significant demands on the cathode as the reaction kinetics are slower than those related to fuel oxidation in the anode or ion migration in the electrolyte. Cathode design and composition are therefore of crucial importance for the cell performance at low temperature. The different approaches that have been adopted for cathode materials research can be broadly classified into the categories of protonic–electronic conductors, oxide-ionic–electronic conductors, triple-conducting oxides, and composite electrodes composed of oxides from two of the other categories. Here, we review the relatively short history of PCFC cathode research, discussing trends, highlights, and recent progress. Current understanding of reaction mechanisms is also discussed.
The zeolitic imidazolate framework-8 (ZIF-8) combines a significantly high microporosity with an excellent thermal, chemical, and hydrothermal stability. Here, we demonstrated that ZIF-8 can display significant levels of protonic conductivity through a water-mediated surface transport mechanism associated to the presence of di-coordinated Zn ions revealed by X-ray photoelectron spectroscopy. A set of powders with particle sizes from 2.8 µm down to 80 nm studied by dynamic water vapour sorption analysis was used to demonstrate that water adsorbs predominantly in the micropore cavities of microcrystalline ZIF-8, whereas adsorption on the external surface becomes the dominant contribution for the nanostructured material. Impedance spectroscopy in turn revealed that the protonic conductivity of the nanocrystalline ZIF-8 was two orders of magnitude higher than that of the micron-sized powders, reaching approximately 0.5 mS·cm−1 at 94 °C and 98% relative humidity. Simple relations were derived in order to estimate the potential gains in water uptake and conductivity as a function of the particle size. This new strategy combining particle nanostructuring with surface defects, demonstrated here for one of the most know metal organic framework, is of general application to potentially boost the conductivity of other materials avoiding chemical functionalization strategies that in most if not all cases compromise their chemical stability, particularly under high humidity and high temperature conditions.
4 February 2019 in Journal of Materials Chemistry A
The utilization of biobased materials for the fabrication of naturally derived ion-exchange membranes is breezing a path to sustainable separators for polymer electrolyte fuel cells (PEFCs). In this investigation, bacterial nanocellulose (BNC, a bacterial polysaccharide) and lignosulfonates (LS, a by-product of the sulfite pulping process), were blended by diffusion of an aqueous solution of the lignin derivative and of the natural-based cross-linker tannic acid into the wet BNC nanofibrous three-dimensional structure, to produce fully biobased ion-exchange membranes. These freestanding separators exhibited good thermal-oxidative stability of up to about 200 °C, in both inert and oxidative atmospheres (N2 and O2, respectively), high mechanical properties with a maximum Young’s modulus of around 8.2 GPa, as well as good moisture-uptake capacity with a maximum value of ca. 78% after 48 h for the membrane with the higher LS content. Moreover, the combination of the conducting LS with the mechanically robust BNC conveyed ionic conductivity to the membranes, namely a maximum of 23 mS cm−1 at 94 °C and 98% relative humidity (RH) (in-plane configuration), that increased with increasing RH. Hence, these robust water-mediated ion conductors represent an environmentally friendly alternative to the conventional ion-exchange membranes for application in PEFCs.
GdBaCo2−xFexO5+δ oxides show crystal structures and ASR values dependent on the composition and synthesis atmosphere. A new modulation of the structure is found for the material with x = 0.6.
23 February 2018 in Journal of Materials Chemistry A
GdBaCo2−xMnxO5+δ is a new system of layered perovskites displaying better electrochemical properties when a layered-type ordering of Gd and Ba cations is adopted.