In this work we investigate the effect of platinum loading and layer thickness on cathode catalyst degradation by a comprehensive in situ and STEM-EDS characterization. To decouple the effect of the platinum loading and layer thickness from each other, the experiments were categorized in two sets, each with cathode loadings varying between 0.1 and 0.4 mgPtcm−2: (i) Samples with a constant Pt/C ratio and thus varying layer thickness, and (ii) samples with varying Pt/C ratios, achieved by dilution with bare carbon, to maintain a constant layer thickness at different platinum loadings. Every MEA was subjected to an accelerated stress test, where the cell was operated for 45,000 cycles between 0.6 and 0.95 V. Regardless of the Pt/C ratio, a higher relative loss in electrochemically active surface area was measured for lower Pt loadings. STEM-EDS measurements showed that Pt was mainly lost close to the cathode—membrane interface by the concentration driven Pt2+ion flux into the membrane. The size of this Pt-depletion zone has shown to be independent on the overall Pt loading and layer thickness, hence causing higher relative Pt loss in low thickness electrodes, as the depletion zone accounts for a larger fraction of the catalyst layer.
This review provides a comprehensive overview on the development of highly active and durable platinum catalysts with ultra-low Pt loadings for polymer electrolyte membrane fuel cells (PEMFCs) through a combined mathematical modeling and experimental work. First, simulation techniques were applied to evaluate the validity of the Tafel approximation for the calculation of the mass activity (MA) and specific activity (SA). A one-dimensional agglomeration model was developed and solved to understand the effects of exchange current density, porosity, agglomerate size, Nafion®film thickness, and Pt loading on the MA and SA. High porosity (> 60%) and agglomerations at high Pt loadings cause the loss of the Tafel approximation and consequently the decrease in MA and SA. A new structure parameter was introduced to estimate the real porous structure using the fractal theory. The volumetric catalyst density was corrected by the fractal dimension (measured by Hg porosimetry), which gave a good agreement with the experimental values. The loading-dependent Tafel equation was then derived, which contains both the utilization and the non-linear scaling factor. Second, activated carbon composite support (ACCS) with optimized surface area, porosity, pore size, and pore size distribution was developed. The hydrophilic/hydrophobic ratio, structural properties (amorphous/crystalline ratio), and the number of active sites were optimized through metal-catalyzed pyrolysis. Stability of ACCS and Pt/ACCS were evaluated using an accelerated stress test (AST). The results indicated that Pt/ACCS showed no significant loss of MA and power density after 5,000 cycles at 1.0–1.5 V, while the commercial Pt/C catalysts showed drastic losses of MA and power density. Finally, monolayers of compressed Pt (core–shell-type Pt3Co1) catalysts were structured by diffusing Co atoms (previously embedded in ACCS) into Pt. Compressive Pt lattice (Pt*) catalysts were synthesized through an annealing procedure developed at the University of South Carolina (USC). The Pt*/ACCS catalyst showed high initial power density (rated) of 0.174 gPtkW−1and high stability (24 mV loss) at 0.8 A cm−2after 30,000 cycles (0.6–1.0 V). The outstanding performance of Pt*/ACCS is due to the synergistic effect of ACCS and compressive Pt*lattice.
more » « less- NSF-PAR ID:
- 10303283
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 167
- Issue:
- 5
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- Article No. 054512
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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