Fabrication of PBI/SPOSS hybrid high-temperature proton exchange membranes using SPAEK as compatibilizer
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We report that while Fe–N–C materials are a promising alternative to platinum for catalysing the oxygen reduction reaction in acidic polymer fuel cells, limited understanding of their operando degradation restricts rational approaches towards improved durability. Here we show that Fe–N–C catalysts initially comprising two distinct FeN x sites (S1 and S2) degrade via the transformation of S1 into iron oxides while the structure and number of S2 were unmodified. Structure–activity correlations drawn from end-of-test 57 Fe Mössbauer spectroscopy reveal that both sites initially contribute to the oxygen reduction reaction activity but only S2 substantially contributes after 50 h of operation. From in situ 57 Fe Mössbauer spectroscopy in inert gas coupled to calculations of the Mössbauer signature of FeN x moieties in different electronic states, we identify S1 to be a high-spin FeN 4 C 12 moiety and S2 a low- or intermediate-spin FeN 4 C 10 moiety. These insights lay the groundwork for rational approaches towards Fe–N–C cathodes with improved durability in acidic fuel cells.
DFT study illuminating modification of the electronic structure and corresponding experimental validation of the enhanced acid mediated HER activity of Co and S doped Ni 2 P.
Fluoroalkyl phosphonic acids are demonstrated to be an efficient radical scavenger for Nafion™, showing a 58% lower fluoride emission rate than the state of the art, cerium.
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Atomically-dispersed iron-nitrogen-carbon (Fe–N–C) catalysts have arisen as promising candidates for replacing the costly precious metal catalysts in fuel cells but still face some grand challenges, such as insufficient site density and durability. Herein, we report a self-assembly method in an aqueous solution to develop an atomically-dispersed iron catalyst with high oxygen reduction reaction (ORR) activity and stability in acidic electrolytes. As determined by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption spectroscopy (XAS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), this benign aqueous synthesis strategy facilitates the formation of homogeneous atomic nitrogen-coordinated iron sites embedded in a popcorn-like porous graphitic carbon matrix. These catalyst properties contribute to the improved ORR kinetic current density and mass transport. By controlling synthesis chemistry, the correlation between structure and property is systematically investigated. In this work, the iron content is the most critical material property and can regulate site density and graphitic carbon structures in the catalyst, impacting catalytic activity and stability. The enhanced performance and durability were examined in both acidic aqueous electrolytes and membrane electrode assemblies.
Device-level stress tests are developed that focus on anode catalyst layer degradation and future anticipated operating conditions, including intermittent load and reduced platinum group metal content. Square-wave cycles with an upper load limit of 2.5 A cm -2 are utilized to screen commercial iridium (Ir) materials. Performance losses are primarily due to decreasing kinetics and are accompanied by catalyst migration into the membrane, worsening catalyst/ionomer integration, and weakening of the catalyst/membrane interface. For ruthenium-containing catalysts, the in situ performances are higher but durabilities lower than Ir baselines, and any performance advantage is lost within the test. Increased loss is likely due to the higher dissolution rate; microscopy confirmed greater degrees of ruthenium migration. For Ir metal or mixed oxides, ex situ activity improvements generally did not translate to in situ performance. The durability, however, is significantly lower and the loss rate increased from 3 (oxide) to 9 (metal) μ V cycle -1 . These results are consistent with historical findings in literature, rationalize the continued use of iridium oxide as a baseline catalyst, and demonstrate that traditional catalyst development approaches may not improve device-level durability when focused on low-cost applications. A shift in focus may therefore be more effective at improving catalyst utilization and lessening load requirements.
An XY segmented cell was developed for low temperature PEM water electrolysis (PEMWE). The system can assess the local performance by enabling in situ measurements of spatial currents and impedances. In this work, we show through experiments, as well as through modelling work, that the porous transport layer (PTL) must be segmented to eliminate crosstalk. Accurate measurements are only possible when crosstalk is fully eliminated. The XY segmented cell is applied to a case study characterizing the impact of a PTL platinum coating void on spatial performance. The localized performance impact of the coating void is found to be orientation specific: coating voids facing the catalyst layer reduce performance significantly more than coating voids facing the flow field. The results suggest that the tolerances for PTL coating uniformity can be lower at the side facing the flow field. The work showcases the feasibility of the XY segmented cell for impact assessment studies. The presented XY segmented cell enables the characterization of spatial phenomena in PEMWE devices and is envisioned to support modeling efforts and the investigation of manufacturing related tolerances for mass produced PEMWE devices.
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Enabling rapid and extensive decarbonization within the electric power and industrial sectors is likely to require high levels of renewable energy deployment, supported by technologies that store and transform renewable electricity into other useful forms. Within hard to decarbonize sectors such as organic chemicals and heavy-duty transportation, the use of low-carbon intensity hydrogen as a fuel and chemical building block is emerging as a near-term alternative to reduce their fossil-fuel dependency. Water splitting electrolysis to produce hydrogen requires only water and electricity as inputs, eliminating the use of natural gas in steam methane reforming, which is the conventional hydrogen production pathway. When powered by low-carbon electricity, electrolysis represents an important pathway towards cross-sectoral decarbonization.