Cobalt-Doped Carbon Nitride Frameworks Obtained from Calcined Aromatic Polyimines as Cathode Catalyst of Anion Exchange Membrane Fuel Cells

Cobalt-doped carbon nitride frameworks (CoNC) were prepared from the calcination of Co-chelated aromatic polyimines (APIM) synthesized from stepwise polymerization of p-phenylene diamine (PDA) and o-phthalaldehyde (OPAl) via Schiff base reactions in the presence of cobalt (II) chloride. The Co-chelated APIM (Co-APIM) precursor converted to CoNC after calcination in two-step heating with the second step performed at 100 °C lower than the first one. The CoNCs demonstrated that its Co, N-co-doped carbonaceous framework contained both graphene and carbon nanotube, as characterized by X-ray diffraction pattern, Raman spectra, and TEM micropictures. CoNCs also revealed a significant ORR peak in the current–voltage polarization cycle and a higher O2 reduction current than that of commercial Pt/C in a linear scanning voltage test in O2-saturated KOH(aq). The calculated e-transferred number even reaches 3.94 in KOH(aq) for the CoNC1000A900 cathode catalyst, which has the highest BET surface area of 393.94 m2 g−1. Single cells of anion exchange membrane fuel cells (AEMFCs) are fabricated using different CoNCs as the cathode catalysts, and CoNC1000A900 demonstrates a peak power density of 374.3 compared to the 334.7 mW cm−2 obtained from the single cell using Pt/C as the cathode catalyst.

Analysis of MEA’s durability under Accelerated Stress Tests that mimic realistic automotive operations

This work aims at studying MEA’s ageing under single operational “mode” accelerated stress tests (AST), that were specifically designed to replicate under hydrogen/air feeding the main stressors of realistic operations in the automotive sector. A methodology for developing AST is here presented and preliminary results about the activity included. In particular, low power and high power functioning have been mimicked in a Zero-Gradient hardware, which allows a reliable materials comparison. Quantities, measurable in-situ and operando, have been tracked during ageing, like cell power, polarization curves, Pt active area, oxygen mass transport resistance, Electrochemical Impedance Spectra. The final objective is to clarify the underlying ageing mechanisms and assess the contribution of each specific operation to the MEA lifetime, focusing in particular on the cathode catalyst layer durability. Moreover, the rate of voltage loss for the new ASTs has been successfully correlated to the degradation observed under a complete driving cycle protocol.

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.

Influence of Cathode Catalyst Layer with SiO2-Coated Pt/Ketjen Black Catalysts on Performance for Polymer Electrolyte Fuel Cells

In this study, we investigated the effect of silica (SiO2) layer included in a cathode catalyst layer (CL) on the performance for polymer electrolyte fuel cells (PEFCs). Porous carbons such as Ketjen black (KB) have been widely used as a support for Pt catalysts in PEFCs. Such KB-supported Pt catalyst (Pt/KB) was used as a cathode CL with low ionomer content (a condition of low proton conductivity). The Pt/KB was then coated with SiO2. In addition, the Pt/KB and SiO2-coated Pt/KB (SiO2-Pt/KB) were measured and analyzed under relative humidity (RH) conditions (100% and 20%). The catalyst ink of SiO2-Pt/KB showed higher stability and dispersion compared to Pt/KB, due to the hydrophilic surface characteristics of SiO2, which act as a binder-like ionomer. The performance of the SiO2-Pt/KB at 100% RH, was significantly lower than that of Pt/KB, whereas the performance of the Pt/KB at 20% RH, was significantly improved by SiO2 coating. This is due to an increase in the proton conductivity, which can be attributed to the hydrophilic properties of SiO2. Based on these results, the effect of SiO2 coating on performance, depending on carbon supports of SiO2-coated Pt/Carbon catalysts, could be evaluated.