Modeling the Effect of Low Pt loading Cathode Catalyst Layer in Polymer Electrolyte Fuel Cells: Part I. Model Formulation and Validation

A model for the cathode catalyst layer (CL) is presented, which is validated with previous experimental data in terms of both performance and oxygen transport resistance. The model includes a 1D macroscopic description of proton, electron and oxygen transport across the thickness, which is locally coupled to a 1D microscopic model that describes oxygen transport toward Pt sites. Oxygen transport from the channel to the CL and ionic transport across the membrane are incorporated through integral boundary conditions. The model is complemented with data of effective transport and electrochemical properties extracted from multiple experimental works. The results show that the contribution of the thin ionomer film and Pt/ionomer interface increases with the inverse of the roughness factor. Whereas the contribution of the water film and the water/ionomer interface increases with the ratio between the geometric area and the surface area of active ionomer. Moreover, it is found that CLs diluted with bare carbon provide lower performance than non-diluted samples due to their lower electrochemical surface area and larger local oxygen transport resistance. Optimized design of non-diluted samples, with a good distribution of the overall oxygen flux among Pt sites, is critical to reduce mass transport losses at low Pt loading.

Ultra-Low Pt Loading in PtCo Catalysts for the Hydrogen Oxidation Reaction: What Role Do Co Nanoparticles Play?

The effect of the nature of the catalyst on the performance and mechanism of the hydrogen oxidation reaction (HOR) is discussed for the first time in this work. HOR is an anodic reaction that takes place in anionic exchange membrane fuel cells (AEMFCs) and hydrogen pumps (HPs). Among the investigated catalysts, Pt exhibited the best performance in the HOR. However, the cost and the availability limit the usage. Co is incorporated as a co-catalyst due to its oxophylic nature. Five different PtCo catalysts with different Pt loading values were synthesized in order to decrease Pt loading. The catalytic activities and the reaction mechanism were studied via electrochemical techniques, and it was found that both features are a function of Pt loading; low-Pt-loading catalysts (Pt loading < 2.7%) led to a high half-wave potential in the hydrogen oxidation reaction, which is related to higher activation energy and an intermediate Tafel slope value, related to a mixed HOR mechanism. However, catalysts with moderate Pt loading (Pt loading > 3.1%) exhibited lower E1/2 than the other catalysts and exhibited a mechanism similar to that of commercial Pt catalysts. Our results demonstrate that Co plays an active role in the HOR, facilitating Hads desorption, which is the rate-determining step (RDS) in the mechanism of the HOR.

Activation of bimetallic PtFe nanoparticles with zeolite-type cesium salts of vanadium-substituted polyoxometallates toward electroreduction of oxygen at low Pt loadings for fuel cells

The catalytic activity of commercial carbon-supported PtFe (PtFe/C) nanoparticles admixed with mesoporous polyoxometalate Cs3H3PMo9V3O40, (POM3-3–9), has been evaluated towards oxygen reduction reaction (ORR) in acid medium. The polyoxometalate cesium salt co-catalyst/co-support has been prepared by titration using the aqueous solution of phosphovanadomolibdic acid. The synthesized material has been characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results confirm formation of the polyoxometalate salt with the characteristic Keggin-type structure. The composite catalyst has been prepared by mixing the POM3-3–9 sample with the commercial PtFe/C by sonication. The diagnostic rotating ring-disk voltammetric studies are consistent with good performance of the system with low Pt loading during ORR. The fuel cell membrane electrode assembly (MEA) utilizing the PtFe/POM-based cathode has exhibited comparable or better performance (at relative humidity on the level of 100, 62, and 17%), in comparison to the commercial MEA with higher Pt loading at the cathode. Furthermore, based on the cell potential and power density polarization curves, noticeable improvements in the fuel cell behavior have been observed at the low relative humidity (17%). Finally, the accelerated stress test, which uses the potential square wave between 0.4 V and 0.8 V, has been performed to evaluate MEA stability for at least 100 h. It has been demonstrated that, after initial losses, the proposed catalytic system seems to retain stable performance and good morphological rigidity.

Intermetallic Platinum Alloy Nanoparticles and Single Atoms Hybrid Electrocatalysts for Proton Exchange Membrane Fuel Cells

Proton exchange membrane fuel cell converts hydrogen and oxygen into electricity with zero emission1. The high cost and low durability of Pt-based electrocatalysts for oxygen reduction reaction hinder its wide applications2,3. The development of non-precious metal electrocatalysts also reaches the bottleneck because of the low activity and durability4,5. Here we rationally design a hybrid electrocatalyst consisting of atomically dispersed Pt and Fe single atoms and intermetallic PtFe alloy nanoparticles. The Pt mass activity of the hybrid catalyst is 3.5 times higher than that of commercial Pt/C in a fuel cell. More importantly, the fuel cell with an ultra-low Pt loading in the cathode (0.015 mgPt cm-2) shows unprecedented durability, with 93.6% activity retention after 100,000 cycles and no noticeable current drop at 0.6 V for at least 206 h. These results highlight the importance of the synergistic effects among active sites in hybrid electrocatalysts and provide an alternative way to design more active and durable low-Pt electrocatalysts for electrochemical devices.