Electrocatalyst Degradation in High Temperature PEM Fuel Cells
Durability and cost are the major limiting factors in current PEM fuel cells development and commercialization. Electrocatalyst materials are the main responsible of both cost of the entire fuel cell stack and its degradation during operation [1,2]. In this research durability and degradation have been investigated in high temperature PEM fuel cells (HT-PEMFCs). Specific diagnostic techniques have been studied and tested for the investigation of electrocatalyst structural properties. An experimental sensibility analysis has been carried out with the purpose to assess advantages and limitations of the use of cyclic voltammetry to determine the electrocatalyst ECSA in H3PO4/PBI high temperature PEM fuel cells. Small angle x-ray scattering (SAXS) has been used to obtain structural information of the electrocatalyst nanoparticles, such as size and distribution. A procedure to characterize HT-PEMFCs MEAs by means of SAXS has been developed and tested. Transmission electron microscopy (TEM) is a complementary technique to SAXS: it has been used to validate the diagnostic method and to compare the results. Electrocatalyst evolution during long-term operation has been studied and related with performance loss. Specific stress test protocols have been developed to accelerate electrocatalyst degradation in commercial HT-PEMFC MEAs operated in single cell configuration. Two MEAs have been subjected to load cycling and one to start/stop cycling. One of the two testing protocols based on load cycling included open circuit (OC) condition in each cycle with the purpose to study the effects of frequent and short OCs during operation on MEA durability and electrocatalyst evolution. Specific start-up and shutdown procedures have been used in the start/stop test in order to limit other degradation mechanisms. Cell voltage and polarization curves have been recorded to monitor cell performance during the durability tests. The electrocatalyst structural evolution induced by load cycling has been characterized with SAXS and TEM. The stress test protocols have been effective to accelerate performance and electrocatalyst degradation of the MEA. The voltage decay rate at 200 mAcm-2 was higher than 25 μVh-1 in the samples subjected to load cycles. The start/stop cycling caused a performance degradation of 18 μV/cycle at 222 mAcm-2 during the first 450 cycles of the test. Regarding the diagnostic techniques used to characterize the electrocatalyst, cyclic voltammetry (CV) seems not to be particularly reliable when performed at high temperatures (>100°C) due to the high dependence of the voltammogram shape to humidity conditions. SAXS, on the other hand, seems to be an effective tool to investigate structural properties of PEMFC electrocatalysts. SAXS analysis showed that after 100,000 load cycles the mean size of the platinum nanoparticles more than doubled. TEM results varied about 30% from the SAXS results: this divergence could be due to a very different population size of the nanoparticles that have been analysed in the two methods. Moreover, the preparation of the sample used in TEM may have strongly influenced the electrocatalyst structure. Finally, a visualization of the electrocatalyst structural evolution on large areas of the MEAs subjected to load cycling showed preferential directions of the particles growth that could be due to the position of the channels on the flow-field plates of the fuel cell.