Fuel Cell Membrane Electrode Assemblies Research Articles

(Invited) Durable and Highly Active Fe-N-C Catalysts for PEM Fuel Cells

Atomically dispersed and nitrogen-coordinated single iron sites (FeN4) embedded in carbon (Fe-N-C) catalysts are the most promising platinum group metal (PGM)-free catalysts. However, they have yet to match their Pt counterparts for oxygen reduction reaction (ORR) activity and stability in proton exchange membrane fuel cells (PEMFCs). Here, we developed viable Fe-N-C catalysts, which, for the first time, demonstrated competitive activity to that of Pt/C catalysts and dramatically enhanced stability and durability under practical PEMFC operating conditions. The most active Fe-N-C catalyst achieved a record half-wave potential (E1/2 = 0.915 V vs. RHE at 0.6 mgcatcm-2) and an ORR mass activity of 10.5 mA mgcat at 0.9 V in (RDE) tests, exceeding a Pt/C baseline catalyst (60 µgPt cm-2) by 40 mV in acidic electrolytes. This compelling activity of the Fe-N-C catalyst in aqueous acids on rotating disk electrode (RDE) was successfully transferred to fuel cell membrane electrode assembly (MEAs), generating an initial current density of 44.2 mA cm-2 exceeding the U.S. DOE 2025 target (i.e., 44 mA cm-2) at 0.9 VIR-free under O2. Under practical hydrogen-air conditions, record 151 mA cm-2 at 0.8 V and peak power density of 601 mW cm-2 were achieved. Importantly, we discovered that depositing nitrogen-carbon species on the catalyst surface via chemical vapor deposition (CVD) dramatically enhanced catalyst stability, evidenced by performance durability after accelerated stress tests (30 000 square-wave voltage cycles under H2/air) and long-term steady-state life tests (> 300 hours at 0.67 V). Innovative identical location-scanning transmission electron microscopy (IL-STEM) experiments confirmed that the CVD process leads to deposition of nitrogen-doped carbon onto the catalyst surfaces. Along with theoretical modeling, a reconstruction of the carbon structure adjacent to FeN4 sites leads to increased robustness against demetallation and carbon oxidation. This work opens new avenues for developing earth-abundant iron-based catalysts with extraordinary activity and stability, thus competing with Pt and addressing the cost barrier of current PEMFCs.

Impact of Reinforced Polymer Electrolyte Membrane Scratch on Fuel Cell Durability Using 4D X-Ray Computed Tomography Technique

PEMFCs, or Polymer Electrolyte Membrane Fuel Cells, can be used in both stationary power and transportation applications and are promising for use in heavy duty electric vehicles due to their high energy density, ability to be refueled quickly, and extended range, which are key challenges for battery-powered vehicles [1]. Despite these advantages, there are still obstacles preventing the widespread commercialization of PEMFCs, one of which is production cost [2]. To reduce manufacturing costs, it is imperative to ensure that quality control rejects and scraps are minimized. Moreover, enhancing component integration defect detection would ensure the durability of the fuel cell and enhance its operational lifetime. However, robust quality control requires a thorough understanding of potential non-uniformities and their effects on fuel cell performance and operational degradation.Non-uniformities of the membrane electrolyte assembly (MEA) can result in durability issues by damaging the membrane and making it more vulnerable to mechanical and chemical stress during the operation [3]. Several studies have been done on cation contamination and membrane pinholes and their effect on fuel cell performance and durability [4,5] but little attention has been paid to other types of non-uniformities such as membrane scratches and foreign particles, which may also conceivably affect durability [6]. By implementing 4D in-situ X-ray computed tomography (XCT) [7,8], the current work aims to track the evolution of scratches that appear on a reinforced membrane surface during fabrication and its specific objective is to determine the impacts of membrane scratches on membrane durability in fuel cells.The study was conducted by using small-scale fuel cells with GORE-SELECT® membranes that were intentionally scratched with a razor blade, subjecting them to combined chemomechanical membrane accelerated stress test (AST), and monitoring the membrane degradation and evolution of the scratches using 4D-XCT throughout the AST. During the fabrication step, the depth of scratches was regulated by a weak bond between the reinforcement layer and the perfluorosulfonic acid (PFSA) layer, i.e., the scratches did not tear through the reinforcement. Furthermore, the scratches did not adversely impact the initial cell performance. However, during AST operation the evolution of the scratched region was affected by several factors, including the friction between the layers of the membrane electrode assembly, the width of the scratch (Figure 1), the presence of membrane debris, and the extent of membrane strain. Additionally, it was observed that changes in the quality of catalyst layer transfer onto the scratched region can alter the degradation pattern and potentially create a self-mitigating mechanism. These findings may be used to develop more optimized quality control measures for membrane scratches in fuel cell production. 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. This research was undertaken, in part, thanks to funding from the Canada Research Chairs program. Keywords: fuel cell; membrane durability; X-ray computed tomography; membrane scratch; manufacturing References [1] Cullen DA, Neyerlin KC, Ahluwalia RK, Mukundan R, More KL, Borup RL, et al. New roads and challenges for fuel cells in heavy-duty transportation. Nat Energy 2021;6:462–74. https://doi.org/10.1038/s41560-021-00775-z.[2] Whiston MM, Azevedo IL, Litster S, Whitefoot KS, Samaras C, Whitacre JF. Expert assessments of the cost and expected future performance of proton exchange membrane fuel cells for vehicles. Proc Natl Acad Sci U S A 2019;116:4899–904.[3] De Bruijn FA, Dam VAT, Janssen GJM. Review: Durability and degradation issues of PEM fuel cell components. Fuel Cells 2008;8:3–22.[4] Tavassoli A, Lim C, Kolodziej J, Lauritzen M, Knights S, Wang GG, et al. Effect of catalyst layer defects on local membrane degradation in polymer electrolyte fuel cells. J Power Sources 2016;322:17–25.[5] Lü W, Liu Z, Wang C, Mao Z, Zhang M. The effects of pinholes on proton exchange membrane fuel cell performance. Int J Energy Res 2011;35:24–30.[6] Kundu S, Fowler MW, Simon LC, Grot S. Morphological features (defects) in fuel cell membrane electrode assemblies. J Power Sources 2006;157:650–6.[7] Ramani D, Singh Y, White RT, Wegener M, Orfino FP, Dutta M, et al. 4D in situ visualization of mechanical degradation evolution in reinforced fuel cell membranes. Int J Hydrogen Energy 2020;45:10089–103.[8] White RT, Eberhardt SH, Singh Y, Haddow T, Dutta M, Orfino FP, et al. Four-dimensional joint visualization of electrode degradation and liquid water distribution inside operating polymer electrolyte fuel cells. Sci Rep 2019;9:1–12. Figure 1

Impact of polymer additives on crack mitigation of rod-coated fuel cell cathode catalyst layers

Cracks in catalyst layers (CLs) are a potential source of long-term failure in a fuel cell membrane electrode assembly (MEA). While modifications to the CL ink formulation can affect the degree of cracking, these changes may lead to lower initial performance than their cracked analogues due to the established link between formulation and performance. In this work, we explored the use of polymeric additives to mitigate CL cracks. Small quantities of poly (acrylic acid), poly (ethylene oxide), poly (methyl methacrylate), or poly (vinyl alcohol) – 5 wt% relative to ionomer mass – were added to the ink prior to its final mixing. Poly (vinyl alcohol) resulted in crack–free CLs, whereas the other polymers resulted in CLs with similar crack percentages as the control CL. Through a combination of transmission electron microscopy, X-ray computed tomography, and infrared spectroscopy, we ascribed the crack–mitigating mechanism of poly (vinyl alcohol) to its ability to hydrogen–bond with Nafion, the ion conducting polymer binder in the catalyst ink. Initial performance of this non–cracked electrode exhibited nearly identical electrochemical behavior to its cracked counterpart, demonstrating that PVA additives successfully reduce cracks while maintaining cell initial performance.

Study of Contact Pressure Distribution in Bolted Encapsulated Proton Exchange Membrane Fuel Cell Membrane Electrode Assembly

The distribution of contact pressure on the Membrane Electrode Assembly (MEA) significantly affects the performance of a Proton Exchange Membrane Fuel Cell (PEMFC). This paper establishes a PEM fuel cell model to investigate the impact of bolt load and its distribution, sealing gasket hardness, and size on the magnitude and distribution of contact pressure on the MEA during assembly. Thermal–mechanical coupling is employed to simulate the thermal effects resulting from chemical reactions under operational conditions. The findings reveal that there is an extremum of pressure uniformity in the range of 5000 to 6250 N for bolt loads. When the average bolt load is lower than this extremum, altering the distribution of the load can effectively enhance the uniform distribution of contact pressure. Stiffer gaskets reduce the contact pressure on the MEA while increasing the pressure on the gasket itself, resulting in reduced deformation. A rational matching relationship among gaskets, Gas Diffusion Layers (GDLs), and seal grooves is proposed. During operational conditions, thermal effects decrease the sealing performance and also impact the magnitude and distribution of contact pressure on the MEA. These outcomes provide significant guidance for the assembly and performance evaluation of PEMFCs.

Fabrication and Scale-up of Highly Durable Heavy Duty Fuel Cell MEAs

Medium and heavy-duty PEM fuel cells operate under much harsher conditions than light duty fuel cells and are expected to last 25,000-30,000 hours in the field. These systems must operate successfully in the presence of impurities, starting and stopping, freezing and thawing, humidity and load cycling. Therefore, materials, components, and interfaces used in such systems must be highly resistant to severe mechanical and chemical stress.Novel, highly active stable Pt and ordered PtCo intermetallic nanoparticles with well-controlled particle size and composition have been synthesized on a highly efficient PGM-free single metal active site rich carbon, to maximize their synergistic effects for enhanced performance and durability. Integrating these catalysts integrated with high O2 permeability ionomer (HOPI) in membrane electrode assemblies (MEAs) improved their fuel cell performance and durability, allowing the MEAs to achieve >600 mA/mgPt at 0.9 VIR-free with a mass activity loss < 30% after 150k square wave accelerated stress test (AST) cycles; and > 600 mA/cm2 (~65% efficiency) at 0.8 V, with a performance loss < 40 mV after 150K AST cycles.In a PEM fuel cell, the catalyst ink formulation and mixing processes control catalyst layer coating quality, electrode morphology, and the resulting fuel cell performance and durability. Catalyst ink properties are a result of complex solvent-catalyst-ionomer interactions that depend on the mixing method employed. Here, we compare the performance and durability of electrodes made from bath sonicated inks for ultrasonic spray coating before and after the catalyst scale up. Ink rheology and catalyst particle size are used to correlate ink properties to electrode morphology and structure and ensure consistency from batch to batch, and from small lab scale to subsequent scale-up. We evaluate and discuss the challenges that arise when transitioning from spray coating catalyst ink on a small scale, directly on a membrane, to coating more viscous inks on gas diffusion layers (GDLs), made via Mayer rod coating of ball milled inks, in anticipation of developing a roll-to-roll (R2R) fabrication process. The MEA performance and durability of the novel catalyst was also evaluated under heavy duty operating conditions using M2FCT’s AST, i.e., in H2/Air, 90 ⁰C, and 50% RH.This work provides a comprehensive understanding of interactions between Pt, PtCo, carbon, ionomer, membrane, and GDLs and their impact on electrode structure, fuel cell performance and durability, as well as considerations for scale up to a R2R fabrication process. The attained information will be used to improve fuel cell electrode design, fabrication and scale-up.Acknowledgement: The project is financially supported by the Department of Energy’s Fuel Cell Technology Office under the Grant DE-SC0021671. Figure 1. (a) Comparison of H2-air fuel cell performance of HOPI-based CCMs prepared with different volume ratios of H2O to n-propanol (nPA). (b) Dependence of fuel cell performance at 0.8 and 0.7 V of the CCMs prepared with different volume ratios of H2O to nPA. (c) MEA performance of the best performing Pt (40 wt. %)/Mn-N-C MEA under various relative humidity. (d) The high-frequency resistance (HFR) of HOPI-based CCMs prepared with a volume ratio of 2:1. All of the tests were performed with a 5 cm2 differential cell with 14 parallel channels. The cell temperature was 80 ⁰C, the flow rates for H2 and air are 500 and 2000 sccm, and the backpressure is 250 kPaabs. The Pt loading in the anode and cathode are 0.1 and 0.2 mgPt/cm2, respectively. Figure 1

Coaxial Nanowire Electrodes Enable Exceptional Fuel Cell Durability.

Polymer electrolyte membrane fuel cells (PEMFCs) hold great promise for applications in clean energy conversion, but cost and durability continue to limit commercialization. This work presents a new class of catalyst/electrode architecture that does not rely on Pt particles or carbon supports, eliminating the primary degradation mechanisms in conventional electrodes, and thereby enabling transformative durability improvements. The coaxial nanowire electrode (CANE) architecture consists of an array of vertically-aligned nanowires, each comprising an ionomer core encapsulated by a nanoscale Pt film. This unique design eliminates the triple phase boundary and replaces it with two double phase boundaries, increasing Pt utilization. It also eliminates the need for carbon support and ionomer binder, enabling improved durability and faster mass transport. Fuel cell membrane electrode assemblies based on CANEs demonstrate extraordinary durability in accelerated stress tests (ASTs), with only 2% and 5% loss in performance after 5,000 support AST cycles and 30,000 catalyst AST cycles, respectively. The high power density and extremely high durability provided by CANEs could enable a paradigm shift from random electrodes based on unstable platinum nanoparticles dispersed on carbon to ordered electrodes based on durable Pt nanofilms, facilitating rapid deployment of fuel cells in transportation and other clean energy applications. This article is protected by copyright. All rights reserved.

Development on Diagnosing Method of Metallic Micro-particles Buried into Fuel Cell Membrane Electrode Assemblies using Electromagnetic Field Excited Oscillation

Development on Diagnosing Method of Metallic Micro-particles Buried into Fuel Cell Membrane Electrode Assemblies using Electromagnetic Field Excited Oscillation

Development on Diagnosing Method of Metallic Micro-particles Buried into Fuel Cell Membrane Electrode Assemblies using Electromagnetic Field Excited Oscillation

Development on Diagnosing Method of Metallic Micro-particles Buried into Fuel Cell Membrane Electrode Assemblies using Electromagnetic Field Excited Oscillation

Dimeric ionic liquid for improving performance and durability of PEMFCs

A dimeric ionic liquid (1,1'-(butane-1,4-diyl)bis9-methylpyrimido[1,2-a]pyrimidinium) di-nonafluorobutanesulfonate (D-MTBD) is investigated for surface modification to a PtCo/C catalyst for improving performance and durability of the catalyst in a fuel cell membrane electrode assembly (MEA). Compared to the PtCo/C catalyst without modification, the addition of the dimeric ionic liquid (IL) improves the mass activity (MA) of the PtCo/C catalyst in the MEA, as well as fuel cell performance. Moreover, the dimeric IL also improves the durability of the PtCo/C catalyst. Thermogravimetry and differential scanning calorimetry were used to evaluate the IL's thermal stability and melting point. The viscosity of the catalyst inks with and without IL were compared. Electrochemically active surface area, impedance, and gas diffusion resistance were evaluated and compared with the PtCo/C catalyst without IL modification. Owing to its higher molecular weight and melting point, the dimeric IL shows potential as a highly stable catalyst modifier. This work shows that the dimeric IL may serve as a replacement to regular monomeric ILs for catalyst surface modification.

Local ageing effects of polymer electrolyte fuel cell membrane electrode assemblies due to accelerated durability testing

AbstractAccelerated durability test (ADT) protocols are useful tools to reduce testing time and development costs of automotive polymer electrolyte fuel cell stacks. Established accelerated stress tests allow comparing individual cell components. However, such tests in general do not allow drawing reliable conclusions on the expected lifetime for a complete stack. In this work, we examine the influence of combined stressors on the ageing behavior of individual cell components operated on stack level. We combine known main stressors for mobile fuel‐cell operation such as dynamic load, temperature and humidity cycling or hydrogen/air fronts during start‐up to develop a new accelerated test protocol. It was applied to an automotive 5‐cell short stack for 460 operating hours (OpH). A second stack was operated in a reference long‐term test for 2300 OpH. Several in situ characterization techniques, such as cyclic voltammetry, and recording the local current density distribution were employed. In addition, post‐mortem analyses, such as focused ion beam scanning electron microscopy imaging, was applied in order to better understand the degradation mechanisms. The results presented here provide an excellent basis for the further development of a new ADT protocol, which will accelerate ageing processes in the fuel cell in a realistic way, i.e. leading to similar degradation characteristics as in long term testing.

Ordered CoPt oxygen reduction catalyst with high performance and durability

A high-performance and durable polymer electrolyte membrane fuel cell cathode catalyst composed of an ordered L1 0 –CoPt core and a thin Pt shell was designed and prepared. Under practical fuel cell membrane electrode assembly testing conditions, the cathode catalyst showed an outstanding initial mass activity of 0.6 A/mg Pt , which satisfies the U.S. Department of Energy performance target while also meeting the durability target of less than 40% loss in mass activity after 30,000 accelerated stress test voltage cycles. The high structural stability of the L1 0 –CoPt@Pt-shell catalyst was confirmed by postmortem materials characterization, and the origin of this robustness was revealed by density functional theory calculations, where the barriers for diffusion of Co atoms were observed to be significantly increased in the ordered intermetallic core. • An intermetallic ORR catalyst was prepared through a scalable impregnation method • Mass activity of 0.6 A/mg Pt and high durability were achieved in fuel cell testing • H 2 /air power density of 0.87 W/cm 2 at 0.67 V was achieved with only 0.1 mgPt/cm 2 • Order-dependent energetics of vacancy-mediated diffusion were evaluated using DFT Fuel cells with high power density and high durability could contribute to the realization of net zero carbon emissions in the transportation sector. The catalyst reported here, which uses atomic-level ordering to stabilize Co within the intermetallic CoPt lattice, achieves higher Co retention and better durability compared with conventional CoPt catalysts. The origins of this high durability were investigated using density functional theory calculations, which revealed significantly higher barriers for Co diffusion in ordered catalysts compared with disordered ones. This new intermetallic catalyst is a promising candidate for deployment in transportation and other clean-energy fuel cell applications. An oxygen reduction reaction catalyst composed of core-shell CoPt nanoparticles possessing an ordered Co–Pt core and Pt shell shows excellent performance and durability in fuel cell testing.

Effects of Catalyst Composition, Loading, and Spray Parameters on the Performance of Unitized Regenerative Fuel Cell Membrane Electrode Assemblies

Proton exchange membrane unitized regenerative fuel cells (PEM-URFCs) combine the ability to both produce power (in fuel cell mode) and generate fuel and oxidant (in electrolysis mode) from the same cell. Compared with discrete fuel cell and electrolyzer systems, URFCs provide the potential for lower mass, volume, and cost. The composition and structure of the bifunctional oxygen catalyst layer (CL), which facilitates the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at the same electrode, significantly affects performance and stability, particularly given the wide potential differences and different mass transport phenomena involved under operation in fuel cell or electrolysis mode. We previously showed bimetallic nanoframes provide bifunctional oxygen electrocatalysts with significantly higher activity compared with monometallic structures, evaluated using a rotating disk electrode configuration.1 Here, we investigated the effects of the oxygen CL composition, loading, and spray parameters on the performance of URFC membrane electrode assemblies (MEAs). Pt black and IrO2 catalysts were combined at different ratios and deposited at different mass loadings. Catalyst layers were sprayed directly onto membranes using an ultrasonic spray system. Within ultrasonically sprayed catalyst layers, higher spray rates resulted in improved fuel cell performance. Higher catalyst loadings improved both fuel cell and electrolyzer performance, but reached a region of diminishing returns at higher loadings. The ratio of the ORR catalyst (Pt) to the OER catalyst (IrO2) modulated the performance in both fuel cell and electrolyzer modes. Different catalyst ratios influence the catalyst utilization at higher loadings. The comparison of URFC performance at same Pt or IrO2 loadings indicates that in addition to the active catalyst itself, the non-catalytically active component influences MEA performance. This result is in line with our previous evaluation of synergistic effects of Pt and IrO2 within rotating disk electrode measurements1 and supports that in addition to the significant effects of catalyst material structure on performance, the electrode structure plays a critical role in fuel cell and electrolyzer performance in URFC MEAs. Repeated switching of URFC MEAs between fuel cell and electrolysis modes indicates that reasonable performance is maintained over the initial cycles within our single cell test configuration. References Godínez-Salomón, F.; Albiter, L.; Mendoza-Cruz, R.; Rhodes, C.P. Bimetallic Two-dimensional Nanoframes: High Activity Acidic Bifunctional Oxygen Reduction and Evolution Electrocatalysts. ACS Appl. Energy Mater. 2020, 3, 2404-2421. http://dx.doi.org/10.1021/acsaem.9b02051

Reduction of Interfacial Gaps and Enhancement of PEM Fuel Cell Performance Via a New CCL|MPL Architecture

A new enhanced architecture for fuel cell membrane electrode assemblies (MEAs) which incorporates deposition of an MPL layer directly on a catalyst coated membrane (CCM) is demonstrated. This modified MPL helps to reduce interfacial gaps present between the catalyst layer and the conventional MPL-coated gas diffusion layer of the MEAs and reduces water accumulation, which ultimately results in higher power densities (Figure 1). Three types of commercial carbon black with different porosity and hydrophilicity were directly deposited on the low loading cathode catalyst layers (0.1 mgPt cm−2) of membrane electrode assemblies (MEAs) used in H2/O2 fuel cells. Among the carbon materials investigated, Acetylene Black- and Vulcan XC72R-based modified MPLs (mass loadings ~ 0 – 1.0 mg cm−2) lead to higher performance in the high current density regions due to their lower porosity and higher hydrophobicity. Detailed information about this approach, preparation and performance characteristics will be discussed during the meeting. Figure 1

Durable and High-Power Iron-Based Cathodes for Proton-Exchange Membrane Fuel Cells

Atomically dispersed and nitrogen-coordinated single iron sites (FeN4) embedded in carbon (Fe-N-C) catalysts are the most promising platinum group metal (PGM)-free catalysts. However, they have yet to match their Pt counterparts for oxygen reduction reaction (ORR) activity and stability in proton exchange membrane fuel cells (PEMFCs). Here, we developed viable Fe-N-C catalysts, which, for the first time, demonstrated competitive activity to that of Pt/C catalysts and dramatically enhanced stability and durability under practical PEMFC operating conditions. The most active Fe-N-C catalyst achieved a record half-wave potential (E1/2 = 0.915 V vs. RHE at 0.6 mgcatcm-2) and an ORR mass activity of 10.5 mA mgcat at 0.9 V in (RDE) tests, exceeding a Pt/C baseline catalyst (60 µgPt cm-2) by 40 mV in acidic electrolytes. This compelling activity of the Fe-N-C catalyst in aqueous acids on rotating disk electrode (RDE) was successfully transferred to a fuel cell membrane electrode assemblies (MEAs), generating an initial current density of 44.2 mA cm-2 exceeding the U.S. DOE 2025 target (i.e., 44 mA cm-2) at 0.9 VIR-free under O2. Under practical hydrogen-air conditions, record 151 mA cm-2 at 0.8 V and peak power density of 601 mW cm-2 were achieved. Importantly, we discovered that depositing nitrogen-carbon species on the catalyst surface via chemical vapor deposition (CVD) dramatically enhanced catalyst stability, evidenced by performance durability after accelerated stress tests (30 000 square-wave voltage cycles under H2/air) and long-term steady-state life tests (> 300 hours at 0.67 V). Innovative identical location-scanning transmission electron microscopy (IL-STEM) experiments confirmed that the CVD process leads to deposition of nitrogen-doped carbon onto the catalyst surfaces. Along with theoretical modeling, a reconstruction of the carbon structure adjacent to FeN4 sites leads to increased robustness against demetallation and carbon oxidation. This work opens new avenues for developing earth-abundant iron-based catalysts with extraordinary activity and stability, thus competing with Pt and addressing the cost barrier of current PEMFCs.

Nitrogen-Doped PtNi Catalysts on Polybenzimidazole-Functionalized Carbon Support for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells.

PtM (M = 3d transition metals) alloys are known as the promising oxygen reduction reaction catalysts and have been considered as the replacement of pure Pt catalysts for the commercialization of proton exchange membrane fuel cells. Although great progress has been made in the past three decades, the performance and durability of PtM catalysts still face stringent challenges from practical applications. Functionalization of a catalyst carbon support with nitrogen-contained groups can add charges onto its surface, which can be utilized to build a more complete ionomer/catalyst interface, to reduce the catalyst particle size, and to improve particle size distribution. Nitriding of PtNi catalysts can effectively improve the catalyst activity and stability by the modification of lattice strain. Hereby, we propose a synergistic approach of combining polybenzimidazole-grafted Vulcan XC72 carbon as the catalyst carbon support and the nitriding of PtNi to develop PtNiN/XC72-polybenzimidazole catalysts. Such PtNiN/XC72-PBI catalysts exhibit the excellent performance of fuel cell membrane electrode assembly (i.e., mass activity, 440 mA mgPt-1; electrochemical surface area, 51 m2 gPt-1; and rated power density, 836 mW cm-2) as well as promising catalyst stability. The developed PtNiN/XC72-PBI meets the US DOE 2020 targets of mass activity for the fuel cell catalysts. This work provides a novel approach and a promising pathway on the development of the catalyst using such a synergistic approach─modification of the catalyst structure by nitrogen doping and functionalization of carbon support by polybenzimidazole for both high performance and high durability.

Research priorities for seasonal energy storage using electrolyzers and fuel cells

Paul A. Kempler is a research assistant professor at the University of Oregon and the Associate Director for the Oregon Center for Electrochemistry (OCE). At the OCE, he has developed three graduate laboratory courses in electrochemistry and electrochemical engineering and serves as the liaison to industry partners. His current research interests include interfacial ion transfer in energy conversion and the technoeconomic analysis of decarbonized energy systems. Paul received his PhD in chemical engineering from the California Institute of Technology for research on catalyst integration and gas evolution in photoelectrochemical cells for water splitting. John James Slack is a senior scientist at Nikola Corporation. John specializes in developing novel materials, studying their interactions, and designing nanostructured architectures within fuel cell cores. In the first two years of his career, he authored two successful proposals worth $2.7 million and has co-authored several patents related to advancing the field of fuel cell membrane electrode assemblies. He is active in the fuel cell community, regularly presenting to the Department of Energy and to the Million Mile Fuel Cell Truck Consortium. John's background is in chemical engineering, and he obtained his PhD at Vanderbilt University in 2019. Andrew M. Baker is a senior scientist at Nikola Corporation. His current research is focused on improving the performance and durability of membrane-electrode-assembly materials and accelerated stress test development for heavy-duty PEM fuel cell applications. Prior to working at Nikola, he was a scientist at Los Alamos National Laboratory. He received his PhD in mechanical engineering from the University of Delaware in 2017.

Activation of bimetallic PtFe nanoparticles with zeolite-type cesium salts of vanadium-substituted polyoxometallates toward electroreduction of oxygen at low Pt loadings for fuel cells

The catalytic activity of commercial carbon-supported PtFe (PtFe/C) nanoparticles admixed with mesoporous polyoxometalate Cs3H3PMo9V3O40, (POM3-3–9), has been evaluated towards oxygen reduction reaction (ORR) in acid medium. The polyoxometalate cesium salt co-catalyst/co-support has been prepared by titration using the aqueous solution of phosphovanadomolibdic acid. The synthesized material has been characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results confirm formation of the polyoxometalate salt with the characteristic Keggin-type structure. The composite catalyst has been prepared by mixing the POM3-3–9 sample with the commercial PtFe/C by sonication. The diagnostic rotating ring-disk voltammetric studies are consistent with good performance of the system with low Pt loading during ORR. The fuel cell membrane electrode assembly (MEA) utilizing the PtFe/POM-based cathode has exhibited comparable or better performance (at relative humidity on the level of 100, 62, and 17%), in comparison to the commercial MEA with higher Pt loading at the cathode. Furthermore, based on the cell potential and power density polarization curves, noticeable improvements in the fuel cell behavior have been observed at the low relative humidity (17%). Finally, the accelerated stress test, which uses the potential square wave between 0.4 V and 0.8 V, has been performed to evaluate MEA stability for at least 100 h. It has been demonstrated that, after initial losses, the proposed catalytic system seems to retain stable performance and good morphological rigidity.

Stabilization of Pt on Carbon Supports Doped with Atomically-Dispersed Metal/Metal-Oxide Additives

The shift in focus of Proton Exchange Membrane Fuel Cell (PEMFC) development for use in heavy-duty truck applications has accelerated the need for highly durable and efficient Membrane Electrode Assemblies (MEA) in order to meet the long lifetime requirements (~30,000 hours of runtime or 1 million mile driving distance) and high efficiency to minimize the total cost of ownership dominated by the H2 fuel cost.1 These requirements for heavy-duty truck are far stringent compared to the light-duty vehicle applications (~8,000 hours of run time). This brings into focus the need to develop highly-durable catalyst and membrane materials to satisfy the longer lifetime demanded by heavy-duty trucks.The primary cause of cell voltage loss in an operating fuel cell largely arises from the electrochemical surface area (ECSA) loss of the Pt-based cathode catalyst layer. Two mechanisms, namely Pt migration/coalescence and dissolution/redeposition are responsible for the coarsening of Pt nanoparticles leading to surface area loss.2,3 In this presentation, we will explore the concept of using metal/metal-oxide (M/MOx) based dopants in the carbon support as additives to mitigate the Pt coarsening behavior. Specifically, we evaluate dopants that are in the form of M/MOx nanoclusters and/or atomically-dispersed M in the graphitic carbon lattice (M-Cy). We will discuss fuel cell MEA results by investigating the stability when subjected to accelerated voltage cycling tests along with a suite of ex situ characterizations to understand the chemical nature of the catalyst materials with dopants. Acknowledgements: This work is partially supported by U.S Department of Energy, Office of Energy Efficiency and Renewable Energy under grant DE-EE0008821. References Marcinkoski, J. et al. Hydrogen Class 8 Long Haul Truck Targets. Subsection of the Electrified Powertrain Roadmap. Technical Targets for Hydrogen-Fueled Long-Haul Tractor-Trailer Trucks. DOE Advanced Truck Technologies 1–31 (2019). Available at: https://www.hydrogen.energy.gov/pdfs/19006_hydrogen_class8_long_haul_truck_targets.pdf. Cherevko, S., Kulyk, N. & Mayrhofer, K. J. J. Durability of platinum-based fuel cell electrocatalysts: Dissolution of bulk and nanoscale platinum. Nano Energy 29, 275–298 (2016). Yu, K. et al. Degradation mechanisms of platinum nanoparticle catalysts in proton exchange membrane fuel cells: The role of particle size. Chem. Mater. 26, 5540–5548 (2014). Figure 1

Experimental Analysis on the Influence of Operating Profiles on High Temperature Polymer Electrolyte Membrane Fuel Cells

The Energy System lab at the University of Trieste has carried out a study to investigate the reduction in performance of high temperature polymer electrolyte membrane (HTPEM) fuel cell membrane electrode assemblies (MEAs) when subjected to different ageing tests. In this study, start and stop cycles, load cycles, open circuit voltage (OCV) permanence and constant load profile were considered. Polarization curves (PC) together with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) data were recorded during the ageing tests to assess the fuel cell performance. In this paper, experimental data are presented to confirm the test methodology previously proposed by the authors and to quantitatively correlate the performance degradation to the operational profiles. It was demonstrated that OCV condition, start and stop and load cycling increase degradation of the MEAs with respect to constant load operation. As expected, the OCV is the operational condition that influences performance degradation the most. Finally, the MEAs were analyzed with synchrotron small angle X-ray scattering (SAXS) technique at the Austrian SAXS beamline at Elettra-Sincrotrone Trieste to analyze the nano-morphological catalyst evolution. As for the catalyst morphology evolution, the ex situ SAXS methodology proposed by the authors is confirmed in its ability to assess the catalyst nanoparticles aggregation.

Seed-Mediated Synthesis and Catalytic ORR Reactivity of Facet-Stable, Monodisperse Platinum Nano-Octahedra

Shape-selective, sub-10 nm-sized metal nanoparticles are of high fundamental and practical interest in catalysis and electrocatalysis, where the surface structure dictates the kinetic properties of the nanomaterials. Unlike their bimetallic analogues, the synthesis of size-controlled, pure Pt octahedral nanocatalysts has remained a formidable chemical challenge. In bimetallic shaped systems, however, the benefit of shape is often convoluted with surface composition in complex ways. In the present work, a seed-templated approach is presented for the preparation of ultrasmall octahedral platinum nanoparticles (Pt NPs), harnessing the effect of monocrystalline anisotropic seeds and strict control of the reduction rate and other physicochemical parameters while avoiding polymers, surfactants, and organic solvents. The procedure yields previously elusive 6.7 nm, strictly single-crystal, Pt NPs with partially truncated octahedral shape and prevalent extended {111} surface facets. Electrochemical measurements using rotating disk electrodes in an acid electrolyte revealed a much higher electrochemical active surface area (ECSA) over the state-of-the-art octahedral Pt NPs, which is ascribed to small-sized, poison-free, and preferentially {111} orientated facets. The dramatic kinetic benefit for the oxygen reduction reaction (ORR) of the octahedral shape over spherical particle shapes of same size is convincingly demonstrated. More important for practical applications is the fact that the intrinsic specific ORR activity is about 2.4-fold higher than commercial optimized spherical Pt NPs deployed in fuel cell cathodes at comparable ORR stability. In doing this analysis, we validate the voltammetric correspondence between Pt single crystals and Pt nanoparticulate materials and highlight the kinetic benefits of limiting the proportion of {100} facets. Prolonged suppression of {100} facet growth in octahedral Pt catalysts is the reason for the unusually high specific activity and fair stability and calls for their integration and testing as cathode catalysts in fuel cell membrane electrode assemblies.