Membrane electrode assembly durability is explored for polymer electrolyte membrane electrolyzers, focusing on catalyst (iridium, Ir) degradation at low loading and dynamic operation. Low catalyst loading and high cell potential are critical to observing durability losses over reasonably short experiments, regardless of test profile. While small losses are seen during steady operation, cycling greatly accelerates performance decreases. Ir dissolution mechanistically drives performance loss, thinning the anode catalyst layer and resulting in increasing kinetic losses during extended operation. While morphological changes to the catalyst layer are found, increasing polarization resistance suggests that degradation at the catalyst/ionomer/membrane interface may also contribute. Electrolyzer operation with model wind and solar profiles results in less severe performance losses compared to triangleand square-wave potential cycling due to the lower cycling frequency of the renewable profiles. However, in both cases kinetics dominated the loss, indicating that higher cycling rates accelerate loss and can be used to project the impact of intermittency on device lifetime. These results suggest that performance losses impact electrolyzers' abilities to operate with low catalyst loading and intermittent inputs, and that a combination of component development and system controls are needed to limit potential and performance loss.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this work, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factor over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ∼5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.

For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm−2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm−2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2− and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

Non-Pt-group metal (non-PGM) materials based on transition metal-nitrogen-carbon (M-N-C) and derived from iron salt and aminoantipyrine (Fe-AAPyr) of mebendazole (Fe-MBZ) were studied for the first time as cathode catalysts in double-chamber microbial fuel cells (DCMFCs). The pH value of the cathode chamber was varied from 6 to 11 to elucidate the activity of those catalysts in acidic to basic conditions. The Fe-AAPyr- and Fe-MBZ-based cathodes were compared to a Pt-based cathode used as a baseline. Pt cathodes performed better at pH 6-7.5 and had similar performances at pH 9 and a substantially lower performance at pH 11 at which Fe-AAPyr and Fe-MBZ demonstrated their best electrocatalytic activity. The power density achieved with Pt constantly decreased from 94-99 μW cm(-2) at pH 6 to 55-57 μW cm(-2) at pH 11. In contrast, the power densities of DCMFs using Fe-AAPyr and Fe-MBZ were 61-68 μW cm(-2) at pH 6, decreased to 51-58 μW cm(-2) at pH 7.5, increased to 65-75 μW cm(-2) at pH 9, and the highest power density was achieved at pH 11 (68-80 μW cm(-2) ). Non-PGM cathode catalysts can be manufactured at the fraction of the cost of the Pt-based ones. The higher performance and lower cost indicates that non-PGM catalysts may be a viable materials choice in large-scale microbial fuel cells.

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