RESUMEN
Ensuring the stable operation of proton exchange membrane fuel cells is conducive to their real-world application. A promising direction for stabilizing electrodes is the stabilization of the ionomer via the formation of surface compounds with graphene. A comprehensive study of the (electrochemical, chemical, and thermal) stability of composites for fuel cell electrodes containing a modifying additive of few-layer graphene was carried out. Electrochemical stability was studied by cycling the potential on a disk electrode for 5000 cycles. Chemical stability was assessed via the resistance of the composites to H2O2 treatment using ion-selective potentiometry. Thermal stability was studied using differential thermal analysis. Composites were characterized by UV-Vis spectroscopy, Raman spectroscopy, EDX, and SEM. It was shown that graphene inhibits Nafion degradation when exposed to heat. Contrariwise, Nafion is corrosive to graphene. During electrochemical and chemical exposure, the determining change for carbon-rich composites is the carbon loss (oxidation) of the carbon material. In the case of carbon-poor composites, the removal of fluorine and sulfur from the Nafion polymer with their partial replacement by oxygen prevails. In all cases, the F/S ratio is stable. The dispersity of Nafion in a sample affects its chemical stability more than the G/Nafion ratio does.
RESUMEN
The stability of Nafion-carbon composites is important for the efficient functioning of fuel cells. The thermal decomposition of Nafion, nanostructured carbon materials, such as multi-walled carbon nanotubes, graphene-like materials, and their composites, have been studied using constant heating rate thermogravimetry in air. Materials were characterized by quantitative and qualitative analysis methods, such as thermogravimetry, X-ray photoelectron spectroscopy, scanning, and transmission electron microscopy with field emission. In Nafion-carbon composites, an increase in the thermal stability of the Nafion polymer is observed due to the formation of surface compounds at the Nafion-carbon interface. In this case, the degree of stabilization is affected by both the component composition of the composite and the structure of the nanocarbon material. The greatest effect was obtained in the case of using thermally expanded graphite (few-layer graphene). Nafion is distributed to a greater extent over the surface of the carbon material due to its high structural accessibility. The most thermally stable composite is Nafion-graphene in a mass ratio of components 1:4 with one stage Nafion degradation at 422 °C, whereas the degradation of pristine Nafion occurs in three stages at 341, 413, and 430 °C. The dependences of thermal stability and features of thermal degradation on the composition and structure of composites are discussed.
RESUMEN
The stability of new membrane-electrode assemblies of a proton-exchange membrane fuel cell with highly porous electrodes and low Pt loading, based on the proton-conducting polymer Nafion, was characterized in conditions of electrochemical aging. A comprehensive study of the effect of the microstructure on the evolution of the electrochemical characteristics of the new assemblies was obtained by voltammetry, electrochemical impedance spectroscopy, X-ray powder diffraction, and scanning electron microscopy. Because high (>70%) porosity provides intensive mass transfer inside an electrode, structural-modifying additives-long carbon nanotubes-were introduced into the new electrodes. PEM fuel cells with electrodes of a conventional composition without carbon nanotubes were used for comparison. The aging of the samples was carried out according to the standard accelerated method in accordance with the DOE (Department of Energy) protocols. The results show two fundamental differences between the degradation of highly porous electrodes and traditional ones: 1. in highly porous electrodes, the size of Pt nanoparticles increases to a lesser extent due to recrystallization; 2. a more intense "washout" of Nafion and an increase in ionic resistance occur in highly porous electrodes. Mechanisms of the evolution of the characteristics of structurally modified electrodes under electrochemical aging are proposed.
RESUMEN
Compositional proton-conducting membranes based on perfluorinated Aquivion®-type copolymers modified by detonation nanodiamonds (DND) with positively charged surfaces were prepared to improve the performance of hydrogen fuel cells. Small-angle neutron scattering (SANS) experiments demonstrated the fine structure in such membranes filled with DND (0-5 wt.%), where the conducting channels typical for Aquivion® membranes are mostly preserved while DND particles (4-5 nm in size) decorated the polymer domains on a submicron scale, according to scanning electron microscopy (SEM) data. With the increase in DND content (0, 0.5, and 2.6 wt.%) the thermogravimetric analysis, potentiometry, potentiodynamic, and potentiotatic curves showed a stabilizing effect of the DNDs on the operational characteristics of the membranes. Membrane-electrode assemblies (MEA), working in the O2/H2 system with the membranes of different compositions, demonstrated improved functional properties of the modified membranes, such as larger operational stability, lower proton resistance, and higher current densities at elevated temperatures in the extended temperature range (22-120 °C) compared to pure membranes without additives.
