Carbon xerogels as Pt catalyst supports for polymer electrolyte membrane fuel-cell applications

Abstract

Carbon xerogels prepared by the resorcinol-formaldehyde (RF) sol–gel method with ambient-pressure drying were explored as Pt catalyst supports for polymer electrolyte membrane (PEM) fuel cells. Carbon xerogel samples without Pt catalyst (CX) were characterized by the N 2 sorption method (BET, BJH, others), and carbon xerogel samples with supported Pt catalyst (Pt/CX) were characterized by thermogravimetry (TGA), powder X-ray diffraction (XRD), electron microscopy (SEM, TEM) and ex situ cyclic voltammetry for thin-film electrode samples supported on glassy carbon and studied in a sulfuric acid electrolyte. Experiments on Pt/CX were made in comparison with commercially obtained samples of Pt catalyst supported on a Vulcan XC-72R carbon black support (Pt/XC-72R). CX samples had high BET surface area with a relatively narrow pore size distribution with a peak pore size near 14 nm. Pt contents for both Pt/CX and Pt/XC-72R were near 20 wt % as determined by TGA. Pt catalyst particles on Pt/CX had a mean diameter near 3.3 nm, slightly larger than for Pt/XC-72R which was near 2.8 nm. Electrochemically active surface areas (ESA) for Pt as determined by ex situ CV measurements of H adsorption/desorption were similar for Pt/XC-72R and Pt/CX but those from CO stripping were slightly higher for Pt/XC-72R than for Pt/CX. Membrane-electrode assemblies (MEAs) were fabricated from both Pt/CX and Pt/XC-72R on Nafion 117 membranes using the decal transfer method, and MEA characteristics and single-cell performance were evaluated via in situ cyclic voltammetry, polarization curve, and current-interrupt and high-frequency impedance methods. In situ CV yielded ESA values for Pt/XC-72R MEAs that were similar to those obtained by ex situ CV in sulfuric acid, but those for Pt/CX MEAs were smaller (by 13–17%), suggesting that access of Nafion electrolyte to Pt particles in Pt/CX electrodes is diminished relative to that for Pt/XC-72R electrodes. Polarization curve analysis at low current density (0.9 V cell voltage) reveals slightly higher intrinsic catalyst activity for the Pt/CX catalyst which may reflect the fact that Pt particle size in these catalysts is slightly higher. Cell performance at higher current densities is slightly lower for Pt/CX than the Pt/XC-72R sample, however after normalization for Pt loading, performance is slightly higher for Pt/CX, particularly in H 2/O 2 and at lower cell temperatures (50 °C). This latter finding may reflect a possible lower mass-transfer resistance in the Pt/CX sample.