Consistent processing and long term stability of CdTe devices

Results of a program to investigate the reliability characteristics of unencapsulated low-cost terrestrial solar cells using accelerated stress testing are presented. A total of seven types of cells were investigated. Results of extended (~ 1 year) bias-temperature stress testing of four cell types were obtained. An additional three cell types, including cells fabricated using the advanced technologies of ribbon-grown silicon and polycrystalline silicon, were subjected to various combinations of bias, temperature cycling stress tests. The spectrum of tests used was based on previous years' work, but differs from that used earlier. An electrical measurement procedure capable of distinguishing small changes in cell electrical parameters was used. Significant degradation was shown by some cell types in some stress tests. Other combinations of cell types and stress tests resulted in no detectable cell degradation. Analysis of the origins of the differences in degradation is continuing. Second quadrant characteristics of some cell types were also investigated in order to establish the electrical behavior of cells which may be exposed to this stress condition in modules deployed in the field.

Proton Exchange Membrane (PEM) failure is one of the key criteria in deciding the durability of the PEM fuel cell system. Physical properties such as ionic conductivity and mechanical properties depend on the microstructure. The microstructure is itself strongly dependent on the water content of the membrane (1, 2). It is therefore important to fully understand the effect of degradation stressors on the morphological changes and water-uptake characteristics in order to improve membrane durability.In this work, standard perfluorosulfonic acid (PFSA) ionomer membranes are subjected to a combined chemical and mechanical accelerated stress test (AST) used for rapid benchmarking of in-situ membrane stability. The degradation stressors in the combined chemical/mechanical AST was previously shown by our group to change the molecular structure and lead to membrane material loss (3). The chemical phase of the AST generates hydroxyl radicals that attack both the side chain and main chain of the polymer, while the mechanically generated stresses due to humidity cycling accelerate mechanical failures. The observed structural changes are anticipated to alter the water-uptake properties of the membrane, as shown previously for ex-situ testing (4). The degradation also alters the morphology, ion exchange capacity, mechanical properties, and proton conductivity of the membrane (5). Water-uptake measurements of partially AST degraded catalyst coated membrane (CCM) samples are carried out at room temperature using a dynamic vapor sorption system. In spite of severe fluoride release and membrane thinning, the water-uptake per unit mass of the AST degraded CCMs is found to be relatively constant. Since the test specimens are CCMs which contain a significant amount of catalyst layer material, an attempt is made to measure and separate the mass of the ionomer by thermogravimetric analysis (TGA). The ionomer material loss throughout the AST process is significant due to fluoride release and ionomer degradation, up to roughly 50% at end-of-life (3). The water-uptake per unit mass of ionomer in the CCM is determined by extracting the ionomer weight obtained by heating the CCM in the TGA chamber. In contrast to the previous results normalized by specimen dry weight, the water-uptake increases significantly per unit mass of the ionomer in the CCM, as shown in Fig. 1. Although the increased water-uptake may indicate enlarged solvated hydrophilic domains in the membrane, which is good for enhanced proton mobility, the proton conductivity is found to decrease (Fig. 1). This may be attributed to a decay in proton concentration due to sulfonic acid functional group loss during side chain degradation. The overall effects of the combined chemical/mechanical AST on the membrane morphology and properties are presented and compared to provide additional insight into the complex degradation mechanism.ACKNOWLEDGMENTSResearch funding provided by Automotive Partnership Canada (APC), Natural Sciences and Engineering Research Council of Canada (NSERC) and Ballard Power Systems (BPS) is gratefully acknowledged. BPS is also acknowledged for providing access to experimental facilities, material samples and technical support. REFERENCES1. J.Benziger, A. Bocarsly, M. J. Cheah, P. Majsztrik, B. Satterfield, and Q. Zhao, in Fuel Cells and Hydrogen Storage 141, Bocarly and Mingos, Editors, p. 85 Springer, Berlin Heidelberg 141 (2011).2. Y. Yang, A. Siu, T. J. Peckham, S. Holdcroft, in Advances in Polymer Sciences 215: Fuel cells 1, G. G. Scherer, Editor p. 55 Springer, Berlin Heidelberg 215 (2008).3. C. Lim, L. Ghassemzadeh, F. Van Hove, M. Lauritzen, J. Kolodziej, G.G. Wang, S. Holdcroft, E. Kjeang, J. Power Sources 257 102 (2014).4. L. Ghassemzadeh and S. Holdcroft, J.Am.Chem.Soc. 135 8181 (2013).5. S. V. Venkatesan and E. Kjeang, 11th International Fuel Cell Science, Engineering and Technology Conference, ASME, Minneapolis, MN (2013).

A specific pilot-scale membrane hybrid treatment system for municipal wastewater treatment

Performance evaluation of a pilot-scale membrane filtration system for oily wastewater treatment: CFD modeling and scale-up design

The next wave of LED lighting technology is likely to be tunable white lighting (TWL) devices which can adjust the colour of the emitted light between warm white (∼ 2700 K) and cool white (∼ 6500 K). This type of lighting system uses LED assemblies of two or more colours each controlled by separate driver channels that independently adjust the current levels to achieve the desired lighting colour. Drivers used in TWL devices are inherently more complex than those found in simple SSL devices, due to the number of electrical components in the driver required to achieve this level of control. The reliability of such lighting systems can only be studied using accelerated stress tests (AST) that accelerate the aging process to time frames that can be accommodated in laboratory testing. This paper describes AST methods and findings developed from AST data that provide insights into the lifetime of the main components of one-channel and multi-channel LED devices. The use of AST protocols to confirm product reliability is necessary to ensure that the technology can meet the performance and lifetime requirements of the intended application.

Degradation issues remain among the main factors impeding the development of commercially viable fuel cell (FC) systems for transportation and stationary power applications. The necessity to keep costs and performances at reasonable levels led to the widespread use of carbon supported platinum (Pt) for electrodes and thin PFSA membranes as electrolyte. Both are quite fragile materials but currently without any convincing alternative. To better understand, and eventually limit degradation mechanisms, several kinds of accelerated stress tests (AST) have been developed targeting each material independently: namely open circuit voltage (OCV) for PFSA membranes, potentiostatic regimes for carbon, and potential cycling for Pt [1, 2]. Other accelerated stress tests corresponding to common fuel cell operation sequences were also proposed like constant current, start/stop, hydrogen starvation/dead-ended anode protocols [3,4], temperature, relative humidity or potential/load cycling, or even freeze/thaw protocols [5]. In this work, we focus on load cycling events, which are very close to the potential cycling performed during AST to study Pt and carbon degradation mechanisms. For obvious reasons, load cycling in actual fuel cell systems and potential cycling in AST are usually performed in overfed conditions [6]: i.e. the fuel cell is supplied with the gas flow rates corresponding to the highest current before the intensity increases. And in most of the cases, the gas flow rates are even permanently kept at the highest values during AST. To avoid supplying fuel and air in excess, most of fuel cell stacks are hybridized either with batteries or supercapacitors (SC) to improve the system dynamics (which in return increases its size and cost). Thanks to hybridization, the FC voltage can drop by a few hundreds of mV per cell during the time needed by the gas supply lines to adapt the flow rates, while batteries or SC keep the system power at the required value. However, the impact of such short reactant starvation events on FC performance and durability is not very well known. Therefore, we performed repeated current Heaviside steps as AST on PEM single cells; typical values were from 0.25 to 0.95 A/cm² (with corresponding FC voltages between 0.65 and 0.8 V). The gas flow rates were set either to the maximum current intensity (with air and H2 stoichiometries of 3 and 1.5 in open-anode or 1 in dead-end mode, respectively) or we let the gas lines adjust the flow rates when the current input changed, which took about half a second (during this time, the FC could fell to about 0.1 V). As shown on the Figure, the performance and electrochemical surface area repeatedly aged significantly slower in the second case, i.e. with short gas starvation events. To better understand this difference, similar experiments were performed in a segmented cell [7] with measurements of local currents, anode and cathode potentials. We observed that local cathode potentials were higher in overfed conditions while they dropped for a short time in the other case due to (most probably) oxygen depletion in the cathode compartment. Local negative currents were also observed sometimes when the load decreased, but since they were not associated to high local potentials, they did not worsen degradation. In the same way, since the FC dynamics were limited most probably by air supply, the anode (and thus cathode) local potentials remained low. These results suggest that FC voltage drops during transients due to short lacks of reactants can improve the durability of the catalyst layer, as well as optimize the system efficiency in terms of hydrogen consumption and air compressor power demand which can be a useful observation for the design of optimized hybridization strategies.

A PEM fuel cell’s durability and lifetime are affected by various degradation phenomena, among which chemical degradation of PEM material exerts the most damage. Chemical degradation of PEM occurs when reactive radicals such as hydroxyl (·OH) and hydroperoxyl (·OOH) are generated from the decomposition of hydrogen peroxide. The radicals chemically attack the main and side chains of the perfluorosulfonic acid-based PEM and change its internal chemical structure. This leads to excessive membrane thinning and pinhole formation that causes higher gas crossover and electrode shorting inside the PEM fuel cell1. The generation of harmful radicals accelerates in the presence of Fenton’s metal, such as iron (Fe)2. Evaluation of PEM fuel cell chemical degradation durability is performed using long-term pure chemical accelerated stress test (AST) under high temperature (T), low relative humidity (RH), and open circuit voltage (OCV) conditions3. Physical characterization of a membrane sample used in a fuel cell can help to visualize and assess damage incurred during an AST. These results, however, fail to encompass the formation rate of radicals and intermediate degradation products generated during the AST3. To overcome these issues, computational fluid dynamics models are developed that simulate the evolution of degraded products and predict the lifetime of PEM fuel cells4,5.The present work aims to develop an in-situ one-dimensional (1-D) transient chemical degradation model that describes reaction-transport phenomena within the membrane electrode assembly (MEA) in the presence of Fe and Ce cations. This work considers mechanically reinforced GORE-SELECT® 15 µm baseline (MemA) and chemically and mechanically reinforced 12 µm (MemB-Ce) membranes. The developed in-situ model simulates pure chemical AST operating conditions with variable Fe ion loading and follows the computational algorithms originally presented by Wong and Kjeang4. The model successfully predicted that side chain scission is followed by main chain unzipping, as reported in the literature6. The evaluation of the change in ionomer structure by chemical degradation was done by computing the temporal concentration profile of intermediate degraded ionomer species, hydrogen peroxide, and membrane thickness reduction. The 1-D model also encapsulates the concentration profile of Fe2+ and Fe3+ ions across the PEM and predicts their temporal distribution throughout the simulated AST duration under OCV conditions. It was observed that the MemA thickness decreased rapidly in the presence of Fe ions, as shown in Figure 1. The computational parameters and results were calibrated and validated using in-house AST results for MEAs with embedded Fe metallic particles, which were shown to completely dissolve during conditioning and hence treated as uniformly distributed Fe cations with an initial concentration of 900 ppm at the beginning-of-life7. The model identified a limiting Fe ion concentration limit of 100 ppm that accentuates the chemical attack. Experimentally, a low Fe concentration of 10 ppm was determined in the baseline MemA, which also reduced the membrane thickness within 1125 h of operation, as shown in Figure 1. It is known that cerium (Ce) ions can scavenge harmful radicals and increase the lifetime of PEM fuel cells8. The model, therefore, simulates the effectiveness of Ce ions in the MemB-Ce membrane and the temporal distribution of Ce3+/Ce4+ ions and shows a lower rate of membrane thickness reduction, as shown in Figure 1. The modelling framework was, therefore, able to predict PEM fuel cell lifetime in conjunction with the transport behaviour of both harmful and beneficial cations as well as their interactions during the chemical degradation process at OCV conditions. Keywords: PEM fuel cell, fuel cell durability, chemical degradation model, in-situ modelling, iron, cerium Acknowledgements This research was supported by the Natural Sciences and Engineering Research Council of Canada, Canada Foundation for Innovation, British Columbia Knowledge Development Fund, Western Economic Diversification Canada, Ballard Power Systems, and W.L. Gore & Associates. It was also undertaken in part thanks to funding from the Canada Research Chairs program. References J. Healy et al., Fuel Cells, 5, 302–308 (2005).S. Kundu, L. C. Simon, and M. W. Fowler, Polym. Degrad. Stab., 93, 214–224 (2008).Y. Singh, F. P. Orfino, M. Dutta, and E. Kjeang, J. Electrochem. Soc., 164, F1331–F1341 (2017).K. H. Wong and E. Kjeang, J. Electrochem. Soc., 161, F823–F832 (2014).R. B. Ferreira, D. S. Falcão, and A. M. F. R. Pinto, Int. J. Hydrogen Energy, 46, 1106–1120 (2021).L. Ghassemzadeh, K. D. Kreuer, J. Maier, and K. Müller, J. Phys. Chem. C, 114, 14635–14645 (2010).N. Kumar et al., ECS Meet. Abstr., MA2023-02, 1919–1919 (2023).S. M. Stewart, D. Spernjak, R. Borup, A. Datye, and F. Garzon, ECS Electrochem. Lett., 3, F19–F22 (2014). Figure 1

The adoption of PEM fuel cells for heavy-duty applications, such as maritime transport, often necessitates the use of liquid hydrogen carriers like methanol due to storage and handling considerations.[1] Methanol reforming is an efficient method to generate hydrogen and CO₂ on-site; however, trace amounts of CO invariably remain in the reformate gas, despite subsequent purification steps such as water-gas shift and selective oxidation.[2,3] These residual CO levels, typically in the low ppm range, significantly exceed the tolerance threshold of platinum-based catalysts on the anode (<0.2 ppm),[4] resulting in catalyst poisoning and diminished cell performance. To address this, RuPt alloy nanoparticles supported on carbon are frequently employed for their enhanced tolerance to CO under reformate conditions.[3] Nevertheless, operational challenges arise as Ruthenium (Ru) leaches from the anode catalyst during prolonged use. This Ru migrates through the membrane and deposits on the cathode, poisoning the Pt/C catalyst and severely inhibiting oxygen reduction reaction (ORR) activity.[3,5]Efforts to mitigate Ru leaching have focused on modifying catalyst surface composition and structure. However, because Ru leaching is a long-term phenomenon, accelerated stress tests (ASTs) are essential for investigating this behavior in a practical timeframe. Traditional MEA-based ASTs, while effective, are hindered by high material requirements, long preparation times, and elevated costs, making them less suitable for early-stage catalyst screening. Additionally, quantifying the total amount of Ru leached has remained a significant challenge.In this study, we developed a robust, material-efficient AST protocol using the rotating disk electrode (RDE) to quantitatively evaluate Ru leaching. Three commercial RuPt catalysts with Ru:Pt atomic ratios of 1:1, 1.5:1, and 2:1 were examined, along with a heat-treated 2:1 ratio catalyst with larger particle size and reduced electrochemical surface area (ECSA). The RDE-based AST involved cyclic voltammetry to simulate catalyst aging, with key parameters such as cycle number (100–1000), scan rate (10–100 mV s⁻¹), and upper potential limit (0.8–0.9 V_RHE) systematically varied. Ru dissolution was quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES) from collected electrolyte samples (0.1M H₂SO₄), and changes in catalyst surface composition were assessed through shifts in CO-oxidation peaks.MEA-based AST measurements were also performed to evaluate the stability of these commercial catalysts and compare the results with those obtained from the RDE protocol. This study examines the correlations between RDE- and MEA-derived stability rankings and discusses the limitations of RDE-based ASTs when applied to practical fuel cell conditions.The validated RDE protocol was further applied to self-synthesized RuPt/C and Ru_corePt_shell materials, providing a reliable and cost-effective approach for assessing Ru leaching during early-stage catalyst development. These findings highlight the potential of the RDE-based AST for advancing PEM fuel cell anode catalysts tailored for reformate hydrogen applications.

Although electrochemical water splitting currently represents a small amount of the US hydrogen supply, its role is expected to grow with the emergence of a hydrogen-based infrastructure.[1] Electrolysis is reasonably cost-competitive with a variety of technologies, including batteries (solid state and flow), pumped hydro, and compressed air.[2] When coupled with renewable energy sources, such as wind and solar, electrochemical water splitting can produce hydrogen using a nearly carbon free pathway.[3] The commercial progress of electrolyzers is limited in part by the cost of the catalyst layer. The oxygen evolution reaction is the focus of electrocatalyst development due to slow kinetics relative to hydrogen evolution; iridium nanoparticles are commonly used to catalyse oxygen evolution, with platinum added to ensure conductivity throughout the catalyst layer. Extended surface nanostructures have previously been developed as electrocatalysts in hydrogen fuel cells, where they have produced an order of magnitude higher specific activity than nanoparticles in oxygen reduction and demonstrated a potential benefit in accelerated stress tests.[4] Extended nanostructures have recently been developed for the oxygen evolution reaction, where a similar specific activity improvement was observed in rotating disk electrode (RDE) half-cells. Catalysts formed by spontaneous galvanic displacement are ideally situated, being able to take advantage of the specific activities generally associated with the catalyst type, while significantly improving upon the traditionally low surface areas of extended surfaces. This approach has been used in forming iridium-nickel and iridium-cobalt nanowires.[5] While nanoparticles have modest site-specific activity in oxygen reduction and evolution, nanoparticle evolution catalysts are at a particular disadvantage with regards to surface area, since carbon supports cannot be used at high potentials. Iridium-cobalt and iridium-nickel nanowires have been synthesized with surface areas of 70 m2 gIr ‒ 1, more than double the nanoparticles. In RDE half-cells, the extended nanostructures produce an oxygen evolution mass activity 7 to 8 times greater throughout the kinetic region. Accelerated stress tests were completed by potential holds and cycling over a variety of conditions to study catalyst degradation and establish standardized testing protocols. Acid treatment has been used to remove excess nickel and cobalt template, improving catalyst durability. Following accelerated stress tests in RDE half-cells, iridium-cobalt and iridium-nickel nanowires exceed the mass activity of nanoparticles by more than an order of magnitude. Membrane electrode assembly (MEA) fabrication of these materials has produced electrolyzers with higher performance than the benchmark device. Recent improvements in MEA performance suggest that the promise of extended surface catalysts observed in half-cells can be realized in the application. [1] R. Forgie, G. Bugosh, K.C. Neyerlin, Z. Liu, P. Strasser, Electrochemical and Solid-State Letters, 13 (2010) B36-B39. [2] K. Harrison, M. Peters, in: U.S. Department of Energy (Ed.), http://www.hydrogen.energy.gov/pdfs/review13/pd031_harrison_2013_o.pdf, 2013. [3] K. Harrison, M. Peters, C. Ainscough, in: U.S. Department of Energy (Ed.), http://www.hydrogen.energy.gov/pdfs/progress13/ii_a_2_harrison_2013.pdf, 2013. [4] S.M. Alia, Y.S. Yan, B.S. Pivovar, Catalysis Science & Technology, 4 (2014) 3589-3600. [5] H. Xu, High-Performance, Long-Lifetime Catalysts for Proton Exchange Membrane Electrolysis, in: U.S. Department of Energy (Ed.), http://www.hydrogen.energy.gov/pdfs/review14/pd103_xu_2014_o.pdf, 2014. Figure 1. Surface areas (x-axis) and site-specific oxygen evolution activities (y-axis) of iridium-cobalt nanowires, iridium-nickel nanoparticles, and iridium nanoparticles prior to (red, blue, black) and following (dark red, dark blue, grey) durability testing in RDE half cells. Arbitrary mass activities (1, 4, 7 A mgIr ‒ 1) are included as solid black lines. Figure 1

FeNC catalysts are promising substitutes of platinum‐type catalysts for the oxygen reduction reaction (ORR). While previous research disclosed that high pyrolysis temperatures are required to achieve good stability, it was identified that a trade‐off needs to be made regarding the active site density. The central question is, if a good stability can also be reached at milder pyrolysis conditions but longer duration retaining more active sites, while enabling the defect‐rich carbon to heal during a long residence time? To address this, a variation of pyrolysis temperatures and durations is used in FeNC fabrication. Carbon morphology and iron species are characterized by Raman spectroscopy and Mössbauer spectroscopy, respectively. Fuel cell (FC) activity and stability data are acquired. The results are compared to ORR activity and selectivity data from rotating ring disc electrode experiments and resulting durability in accelerated stress tests mimicking the load cycle and start‐up and shut‐down cycle conditions. It is discussed how pyrolysis temperature and duration affect FC activity and stability. But, more important, the results connect the pyrolysis conditions to the required accelerated stress test protocol combination to enable a prediction of the catalyst stability in fuel cells.

For the use of polymer electrolyte membrane fuel cells (PEMFCs) in heavy duty applications, on-site generation of hydrogen rich gas by reforming hydrocarbons or methanol are a suitable alternative to pure H2 due to higher availability and higher energy density of hydrocarbon fuels [1]. The so-called reformate contains in addition of H2 also CO, which is a catalyst poison. PtRu alloys are the most promising catalysts for PEM fuel cells operated with reformate due to their high CO-tolerance [2]. It is known that the less noble Ru is unstable in acidic PEMFC conditions and is lowering the durability of the membrane electrode assembly (MEA) by dissolution and crossing over through the membrane to the cathode [3]. Ru dissolution and crossover result in a decreased CO-tolerance on the anode and a lower activity of the cathode towards oxygen reduction due to Ru blocking the Pt surface of the cathode catalyst [4]. To prolong the lifetime and CO-tolerance of reformate PEMFCs, the stability of the anode catalysts must be improved. One approach is nano-structuring the catalysts by encapsulating the less noble Ru-core with a Pt-shell. In doing so, the corrosion resistant Pt-shell supposes to protect the Ru-core from dissolution and thus mitigates the Ru crossover phenomenon.In this work, the influence of the Pt-shell thickness on the stability and performance of the Ru@Pt catalysts is investigated. Two catalysts with varying Pt-shell thicknesses were synthesized on Vulcan XC72R carbon via a two-step polyol. The catalyst with the thinner Pt-shell is called Ru@1Pt and with the thicker shell Ru@2Pt. The as-synthesized catalysts were physically characterized by XRD, ICP-OES, TEM and EDS. A representative EDS map of Ru@1Pt is shown in fig. 1a. The physical characterization of the obtained catalysts unveils a Ru@Pt core-shell structure with crystalline hcp Ru and fcc Pt. To further investigate the catalysts electrochemically, MEAs were manufactured using Ru@Pt catalysts as anodes and commercial membranes and cathode catalysts. An accelerated stress test (AST) was developed to target Ru dissolution by potential cycling and was applied to investigate and compare the stability of the catalysts. The MEAs were electrochemically characterized by cyclic voltammetry, CO-stripping and U-I curves before, during and after the AST. Post-mortem cross-section STEM analysis of the stressed cells were performed to evaluate the elemental composition and morphology of the anode and cathode after the stress test.During the AST, CO-stripping on the Ru@1Pt anode showed a peak shift to higher potentials, indicating a decrease in CO-tolerance due to Ru loss. By contrast, on the Ru@2Pt anode, the peak shifted to lower potentials implying a stronger promoting influence of Ru. On the cathode side, CV measurements before and after the AST revealed a double layer increase and a decrease in the HUPD. This change implies the poisoning of Pt with Ru and were more pronounced for Ru@1Pt compared to Ru@2Pt. As seen by the CO-stripping and CV results, the Ru dissolution and crossover was more severe for Ru@1Pt than for Ru@2Pt. Hence, a higher fuel cell performance loss was observed for the cell with Ru@1Pt in H2, as can be seen in fig. 1b. In addition, further U-I curves were measured under varying reformate conditions to identify the influence of CO on the cell performance. Cross-section EDS maps of the stressed MEAs were used to evaluate the Ru dissolution and its distribution in the different layers of the MEA. A higher Ru:Pt ratio was found on the cathode for the cell with Ru@1Pt compared to a cell with Ru@2Pt, which further verifies a higher degree of Ru crossover for the catalyst with the thinner Pt-shell. The above findings could evidence that the shell thickness plays a significant role in the corrosion resistance of core-shell reformate anode fuel cell catalysts.

Platinum-cobalt alloy nanoparticles are of great interest as cathode catalysts for PEMFCs as they have been shown to have enhanced activity versus platinum. However, their relative stability against loss of electrochemically-active surface area in relation to Pt catalysts is still debated. In this study, the evolutions of Pt3Co particle size distributions (PSDs) in fuel cell and aqueous environments were followed during accelerated stress tests (ASTs) using in-operando ASAXS. The measured evolutions showed a degradation mechanism dominated by loss of particles smaller than the critical particle diameter (<5.2 to 6.1 nm, CPD), which depended on environment and the AST. These evolutions were compared to that of a Pt catalyst with a similar initial PSD, which was found to have a lower degradation rate than Pt3Co. The ASAXS data, as well as data from aqueous dissolution, X-ray absorption spectroscopy, individual particle energy-dispersive spectroscopy, X-ray fluorescence spectrometry, and kinetic Monte Carlo calculations support a loss mechanism of increased Pt dissolution from Pt3Co versus Pt due to destabilization caused by extensive dealloying of particles <∼5 nm during ASTs.

The scarcity of iridium, needed to catalyze the sluggish oxygen evolution reaction (OER), hinders large-scale hydrogen production with proton exchange membrane water electrolyzers (PEMWEs). Crucial steps require reducing its loading while improving its overall activity and stability. Despite knowledge transfer challenges, cost and time constraints still favor aqueous model systems (AMSs) over real devices for the OER electrocatalyst testing. During AMS testing, benchmarking strategies such as accelerated stress tests (ASTs) aim at improving catalyst lifetime estimation compared to constant current loads. This study systematically evaluates a commercial Ir catalyst by modifying both AST parameters and the employed backing electrodes to examine their impact on activity-stability relationships. A comprehensive set of spectroscopy and microscopy techniques, including in situ inductively coupled plasma mass spectrometry, is employed to monitor Ir and backing electrode modifications. Our findings demonstrate that the choice of both lower potential limit (LPL) in ASTs and backing electrode significantly influences the estimation of Ir-based electrocatalysts' activity and stability. Unique degradation mechanisms, such as passivation, redeposition on active sites, and contribution to the OER, were observed for different backing electrodes at varying LPLs. These results emphasize the importance of optimizing parameters and electrode selection in ASTs to accurately assess the electrocatalyst performance. Furthermore, they establish the foundation for developing relevant standardized test protocols, enabling the cost-effective development of high-performance catalysts for PEMWE applications.

Polymer electrolyte membrane fuel cells (PEMFCs) has been widely considered as the most promising power sources for electric vehicles due to their ultimate cleanness, high efficiency and fast refueling. Recently, the increased scalability of power and energy in fuel cells has made the PEMFC an ideal power plant for heavy-duty vehicles (HDVs), i.e., electric long-haul trucks and coaches, with different drive cycles and operating conditions, which requires more durable catalyst and membrane compared with light duty vehicles (LDVs). Unfortunately, the degradation mechanism of the catalyst and membrane in membrane electrode assembly (MEA) of PEMFCs during long-period operation under the HDV condition is still not clearly understood. In this work, MEAs were made of our highly active catalysts, 30wt% Pt/KB, as the cathode and a commercial Pt/C catalyst as the anode. The MEAs were tested at different relative humilities under the HDV conditions with catalyst loading of 0.2 mgPt/cm2, back pressure of 250 kPa, under the standard protocol of accelerated stress test (AST) for 180k cycles, which is equivalent to 30,000 h. The results show that the MEA exhibit very high performance at beginning of life (BOL) with a current density of 1.6 A/cm2 at the cell voltage of 0.7 V, high mass activity of 384 mA·mgPt and large electrochemical active surface area (ECSA) of 86 m2·gPt at 50%RH. Under the same testing condition, the MEA still maintained the current density of 1.4 A/cm2, 1.2 A/cm2 and 1.0 A/cm2 and 0.9 A/cm2 at the cell voltage of 0.7 V after the AST of 30k, 60k, 90k and 120k cycles. Moreover, the performance of the MEA significantly decreased to 0.5 A/cm2 and 0.3 A/cm2 at the voltage of 0.7 V after the AST of 150k and 180k cycles. In comparison, the mass activity of the MEA first significantly dropped to 183 mA·mgPt after the AST of 30k cycles and maintains uniform decreasing from 60k cycles to 180 cycles, the similar phenomenon was observed in the degradation of ECSA. The H2 crossover and AC impendence spectra of the MEA was measured at different cell voltage during the AST process, in order to study the kinetic and mass transport loss during the degradation. Furthermore, the Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) was performed on the produced water of the MEA to monitor the degradation of Pt nanoparticles, carbon support, ionomer, and membrane. Besides, the Pt migrations, the pore structure and volume change in the carbon support before and after the AST of 180k cycles were studied using HR-TEM and mercury intrusion porosimetry (MIP). During the whole AST testing cycles, the MEA exhibited higher performance at relatively low humidity level, which is associated with the insufficient hydrophilicity of the carbon support and is more favorable for the PEMFCs working in low-humidity condition. In summary, this work presents the degradation behavior and mechanism for highly efficient and durable PGM-catalyst MEA under HDV conditions.

For proton exchange membrane fuel cells (PEMFC), cathode catalyst durability is presently a key limiting factor to commercialization for automotive applications. The oxygen reduction reaction takes place on the cathode – transforming O2 + 4H+ + 4e- to 2H2O. Degradation occurs during normal operational load profiles for idle-to-peak power transients (rapid stop-go drive cycles), as the cathode voltage quickly switches from 0.9-1.2V (idle) to ~0.6V (peak). Cathode catalyst durability is dependent upon multiple operational factors, including; potential limits, temperature, and pH. As a result of the transient potentials, the electrochemical surface area (ECSA) of the carbon supported platinum catalyst (Pt/C) is reduced, due to a combination of Pt dissolution, Pt particle growth (migration and/or redeposition), and carbon corrosion (Pt detachment). Typically, accelerated stress tests (AST) are performed on thin films to evaluate catalyst durability and decouple contributions from ancillary fuel cell materials and structures. The thin films consists of catalyst deposited on a conductive rotating disk electrode and analyzed in liquid electrolyte (HClO4 or H2SO4) vs. a separate counter and reference electrode – ex-situ to the actual PEMFC environment. This removes the additional complexity of the catalyst layers 3-deminsional structure (containing both Pt/C and proton conducting ionomer), diffusion media and membrane – in-situ. The AST used in this study includes 25,000 potential cycles from idle to peak potential limits using either square or triangular waveforms (SW or TW, respectively) at 10 sec intervals, for both Pt/C thin films and catalyst layers. ECSA was measured periodically during the cycles, either by integration of the hydrogen desorption area or by CO stripping analysis. The following operational limits were used with a lower potential limit of 0.6V – several upper potential limits (UPL) from 0.9 to 1.2V, multiple temperature ranges between 25°C and 70°C, and different electrolyte pH ranges 0 to 1. Ex-situ AST results in 0.1 M HClO4 at 70°C show that the loss in ECSA was affected by both the UPL and the potential wave profile. For the 0.9V UPL dominated by Pt dissolution, the SW was more aggressive than the TW, resulting in a 45.6% and 36.8% ECSA loss, respectively. While the higher UPL of 1.2V had nearly identical ECSA losses for both potential wave profiles of 89%, due to the dominance of carbon corrosion. Figure 1A shows the effects of pH on AST induced ECSA losses at room temperature for the UPL of 1.2V using a TW. The pH values correspond to different concentrations of HClO4 (0.1 M HClO4 = pH of 1). As the pH is lowered there is an increase in ECSA loss. In Figure 1B the TW was found to cause more catalyst degradation at lower pH values. This potentially could be related to in-situ relative humidity dependent degradation – to be further studied in-situ on a catalyst layer. Figure 1