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At least 19 records

Durability of Pt-Alloy Catalyst for Heavy-Duty Polymer Electrolyte Fuel Cell Applications under Realistic Conditions

As an emerging technology, polymer electrolyte fuel cells (PEFCs) powered by clean hydrogen can be a great source of renewable power generation with flexible utilization because of high gravimetric energy density of hydrogen. To be used in real-life applications, PEFCs need to maintain their performance for long-term use under a wide range of conditions. Therefore, it's important to understand the degradation of the PEFC under protocols that are closely related to the catalyst lifetime. Alloying Pt with transitional metal improves catalyst activity. It is also crucial to understand Pt alloys degradation mechanisms to improve their durability. To study durability of Pt alloys, accelerated stress tests (ASTs) are performed on Pt-Co catalyst supported on two types of carbon. Two different AST protocols were being studied: Membrane Electrolyte Assembly (MEA) AST based on the protocol introduced by the Million Mile Fuel Cell Truck consortium in 2023 and Catalyst AST, adopted from the U.S. Department of Energy (DoE).

25 ENERGY STORAGE

Durability of PGM catalyst MEAs of polymer electrolyte membrane fuel cells for heavy-duty vehicles

Polymer electrolyte membrane fuel cells (PEMFCs) are promising power sources for heavy-duty vehicles (HDVs) owing to cleanliness and efficiency. However, the degradation of membrane electrode assemblies (MEAs) under HDV conditions remains a huge challenge. Here, this work investigated MEA durability under HDV conditions using a US Department of Energy standard accelerated stress test for 180,000 cycles (equivalent to 1 million miles of HDV operation). Effects of catalyst Pt content on MEA durability were examined using homemade 30% Pt/C (H-Pt/C) and commercial 46% Pt/C (C-Pt/C) catalysts. Both MEAs experienced H 2 /air and H 2 /O 2 performance loss over cycles. Analysis with scanning transmission electron microscopy, X-ray diffraction, inductively coupled plasma mass spectrometry, and mercury intrusion porosimetry revealed severe degradation of Pt nanoparticles (NPs), support structures, and the catalyst layer. Two degradation stages for NPs were proposed: Ostwald ripening dominated the initial 60,000 cycles, followed by combined Ostwald ripening and particle migration. Measurements with ion chromatography, high-frequency resistance, and oxygen-diffusion resistance revealed degradation of membrane and ionomer, respectively.

25 ENERGY STORAGE

Dynamic sparse x-ray nanotomography reveals ionomer hydration mechanism in polymer electrolyte fuel-cell catalyst

Tomographic imaging of time-evolving samples is a challenging yet important task for various research fields. At the nanoscale, current approaches face limitations of measurement speed or resolution due to lengthy acquisitions. We developed a dynamic nanotomography technique based on sparse dynamic imaging and 4D tomography modeling. We demonstrated the technique, using ptychographic x-ray computed tomography as its imaging modality, on resolving the in situ hydration process of polymer electrolyte fuel cell (PEFC) catalyst. The technique provides a 40-time increase in temporal resolution compared to conventional approaches, yielding 28 nm half-period spatial and 12 min temporal resolution. The results allow a quantitative characterization of the water intake process inside PEFC catalysts with nanoscale resolution, which is crucial for understanding their electrochemical mechanisms and optimizing their performance. Our technique enables high-speed operando nanotomography studies and paves the way for wider application of dynamic tomography at the nanoscale.

Science & Technology - Other Topics

The impact of hot-press conditions on the durability of polymer electrolyte membrane fuel cells

The proton exchange membrane integrity can be compromised during hot-press fabrication of membrane electrode assemblies (MEAs) causing premature cell failures during operation. In this work, infrared (IR) thermography was used as a diagnostic tool to spatially visualize hydrogen (H 2 ) crossover and identify process-induced-membrane irregularities (PIMs). These irregularities were identified as seed locations for MEA failures. Fine tuning of hot-press conditions was used to mitigate premature cell failures informed by accelerated stress testing (AST). The impact of PIMs on the initial performance, high-frequency resistances, open-circuit voltage, and H 2 crossover are reported. Nafion XL and 212 membranes, hot-pressed with a force of 16 kg/cm 2 and temperature of 120°C, were found to be consistently irregularity-free. Irregularity-free MEAs using Nafion 211, 212, and XL membranes demonstrated AST lifetime improvements of 58, 64 and 400%, respectively, compared to those fabricated with non-optimized conditions. In conclusion, this work highlights the importance of fabrication parameters on premature cell failures.

08 HYDROGEN

Hierarchical low Pt-loading “core-shell” electrocatalysts for the oxygen reduction reaction in fuel cells

The sluggish kinetics of the oxygen reduction reaction (ORR) hinder cost-effective polymer electrolyte fuel cells (PEFCs), which rely on scarce, expensive platinum-based electrocatalysts (ECs). Here, we present a novel synthesis method for ORR ECs achieving exceptional platinum utilization. The design features a hierarchical “multi-carbon” support comprising carbon nanoparticles interacting with graphene nanoplatelets as the “core”, encapsulated by a porous carbon nitride (CN) “shell”. This configuration promotes strong core/shell interactions and a bimodal active site distribution, consisting of chemically dispersed Pt and Ni single-atom complexes and PtNix alloy nanoclusters embedded in the CN shell. These advantages enable high activity and durability, achieving an ORR activity of 1.6 A mgPt−1 at 0.9 V vs. RHE-an order of magnitude higher than Pt/C (0.17 A mgPt−1). A proof-of-concept PEFC demonstrates a specific power of 12.0 kW gPt−1 at 0.60 V. This approach offers a significant step toward more efficient and sustainable PEFC technologies.

Pagot, Gioele [University of Padova, Italy]

Stable Diacid Coordinated Quaternary Ammonium Polymers for 80-230 °C Fuel Cells

Current automotive fuel cells that use sulfonated polymer-based proton exchange membranes are challenging to operate at > 100 °C without humidification. In this project, we developed polymer electrolyte fuel cells that run at > 100 °C without humidification using a novel class of proton exchange membranes made from thermos-oxidatively stable acid-coordinated quaternary ammonium polymers. These fuel cells remove the external humidifiers/demisters and reduce the size of radiators, thus vastly simplifying fuel cell integration, which increases tolerance to impurities and improves electrode kinetics of catalysts. Operating fuel cells without hydration has a significant benefit on fuel cell cost and economic feasibility was investigated by comparing existing fuel cell systems. This project bridges the scale-up process to manufacture the fuel cell component through the U.S. DOE L’Innovator project sponsored by the U.S. DOE Hydrogen and Fuel Cell Technologies Office (HFTO).

30 DIRECT ENERGY CONVERSION

Regulating in situ gaseous deposition to construct highly durable Fe–N–C oxygen-reduction fuel cell catalysts

The activity–stability trade-off challenges the design of high-performance atomically dispersed iron–nitrogen–carbon (Fe–N–C) catalysts for the acidic oxygen reduction reaction in polymer electrolyte fuel cells. Here we develop an in situ chemical vapour deposition approach during catalyst synthesis to break the trade-off, producing highly stable Fe–N–C catalysts while maintaining adequate oxygen reduction reaction activity. The optimal catalyst exhibits a half-wave potential of 0.867 V, remaining unchanged after an accelerated stress test (AST) of 100,000 potential cycles in rotating disk electrode tests. In membrane electrode assemblies under H 2 –air conditions, it delivers 93 mA cm −2 at 0.8 V after a standard AST of 30,000 voltage cycles, and shows minimal current density losses (2.9% at 0.6 V; 14.2% at 0.7 V) after an extended AST up to 120,000 cycles. Furthermore, the catalyst’s durability improvement is primarily due to the in situ chemical vapour deposition, which strengthens Fe–N bonds, increases active-site density, mitigates iron aggregates and reduces surface porosity.

Chemical engineering

Hydrogen Carriers for Renewable Microgrid System Applications

Utility-scale energy storage can help improve grid reliability, reduce costs, and promote faster adoption of intermittent sources such as solar and wind. This paper analyzes the technical aspects and economics of standalone microgrids operating on intermittent power combined with hydrogen energy storage. It explores the feasibility of using dibenzyltoluene (DBT) as a liquid organic hydrogen carrier to absorb excess energy during periods of high supply and polymer electrolyte fuel cells to generate electrical energy during periods of low supply. A comparative analysis is conducted on three power demand scenarios (industrial, residential, and office), in conjunction with three alternative energy sources: solar, wind and wind–solar mix. A mixed system of solar and wind energy can maintain an annual average efficiency above 70%, except for residential power demand, which lowered the efficiency to 67%. A balanced combination of wind and solar power was the most cost-effective option. The current levelized cost of electricity (LCOE) for industrial power demand was estimated to 15 ¢/kWh, and it is projected to decrease to 9 ¢/kWh in the future. For residential power demand, the LCOE was 45% higher due to the demand profile. In comparison, battery storage is significantly more expensive than hydrogen storage, even with future cost projections, increasing the LCOE between 60 and 120 ¢/kWh.

PEM electrolysis

Hybrid Fuel Cell Systems for Heavy-Duty Trucks: Configuration, Heat Rejection, and Performance

Low-temperature polymer electrolyte membrane fuel cell systems can achieve higher efficiency than diesel engines, but heat rejection remains a major challenge in class-8 heavy-duty fuel cell trucks. For the same rated power, the radiator heat load is greater than that in a diesel engine, while the allowable operating temperatures are lower. This work proposes and evaluates 400 kWe fuel cell–battery hybrid (FCH) platforms and operating strategies that manage heat rejection without enlarging the radiator frontal area. Three FCH platforms are identified, each varying in fuel cell system (FCS) rated power, battery energy storage system (ESS) capacity, and maximum stack coolant exit temperature (T h1 ). All three satisfy key system and vehicle requirements, including 175 kWe FCS power at top sustained speed, 400 kWe FCH power on a 6% grade climb, a target stack power density (PD) of 750 mW e /cm 2 , and heat rejection constraints. The first FCH has the smallest FCS, the largest ESS, and a T h1 of 90 °C. The second achieves the highest PD of 840 mW e /cm 2 at a T h1 of 95 °C. The third has the largest FCS, the smallest ESS, and a T h1 of 102 °C. At a Th1 of 115 °C, the platform can be configured as a stand-alone 400 kWe(net) FCS without hybridization, but the achievable PD drops to 460 mW e /cm 2 .

25 ENERGY STORAGE

Mitigating Crack Formation When Using High Oxygen Permeability Ionomer in PEMFC Catalyst Layers

High oxygen permeability ionomers (HOPIs) are being developed as an alternative to conventional perfluorosulfonic (PFSA) ionomers for cathodes in proton exchange membrane fuel cells (PEMFCs). HOPIs aim to reduce local oxygen transport resistance, improving performance and reducing degradation as the catalyst loses surface area. However, HOPIs' more rigid, 3D backbone leads to increased crack density in the cathode, potentially causing accelerated degradation. This study investigates crack formation in HOPI-based and PFSA-bound catalyst layers (CLs). We conducted a comprehensive parametric study to identify conditions and catalyst slurry components that minimize cracking. CLs were fabricated with various ionomer and catalyst types, under different relative humidity (RH) levels, solids weight percentages, solvent ratios, and ionomer-to-carbon ratios (I/C). Results show that HOPI-based CLs exhibit less cracking when fabricated under low RH conditions, with lower solids weight percentage, higher alcohol content, and lower I/C. Additionally, catalysts with low/medium surface area carbon supports show less cracking than those with high surface area carbon supports.

08 HYDROGEN

Quantification of [MTBD][beti] loading and its effects on Pt/HSC electrode performance in hydrogen fuel cells

High surface area carbon-supported platinum catalysts (Pt/HSC) are widely used in polymer electrolyte membrane fuel cells but often suffer from limited proton and oxygen transport within porous domains. To address these challenges, we integrate the ionic liquid [MTBD][beti] into Pt/HSC catalyst layers using two deposition methods-one-pot and sequential deposition-to tune IL distribution within micropores and mesopores. A combination of ex situ and in operando techniques were employed to elucidate electrode structure-performance relationships across a range of IL loadings. Sequential deposition achieved more efficient pore filling and higher IL retention at lower IL:C ratios, enabling enhanced proton conductivity and protection of active sites. Compared to the IL-free Pt/HSC, IL-modified electrodes demonstrated up to 28% improvement in mass activity and enhanced high-current-density performance under low relative humidity, while maintaining comparable performance under humidified conditions. Electrochemical impedance spectroscopy and CO displacement experiments reveal that improvements are linked to reduced ionic resistance and lower sulfonate adsorption on Pt sites, rather than changes in electrochemical surface area. However, excessive IL loading leads to mass transport losses. These results highlight the importance of selective pore filling and efficient IL distribution in achieving kinetic gains without compromising ionic and gas transport.

08 HYDROGEN

Fuel cells for single-aisle regional aircraft: System configuration, performance and cost

A hydrogen fuel cell propelled electric aircraft can compete with incumbent turbofan technologies for single-aisle regional aircraft by coupling design of stack, air handling, thermal management, propulsion, and airframe to optimize performance. The stack operates at 95°C to facilitate heat rejection during take-off and below 75°C during cruise to extend lifetime and is oversized to satisfy power requirements at end of life. A multi-stage turbocompressor with a compression ratio >10 is selected to reach high stack power density at 11,300-m cruise altitude. The propulsion system is configured to accommodate air handling within the core duct, an inclined heat exchanger in the outer duct to limit the nacelle size, and variable area nozzles to independently control mass flows through the core and bypass ducts. The airframe is modified for maximum lift coefficient and longer balanced field length for dramatically reduced thrust during take-off, and the fuselage is stretched by 20% to store liquid hydrogen (LH 2 ). Modularization of power systems promotes safety in one engine inoperative scenarios and allows reaching specific power metrics for stack, balance-of-plant and fuel cell system (FCS), necessary for acceptable take-off weight. In conclusion, cost parity requires increase in FCS lifetime, LH 2 cost reduction, and improved FCS specific power.

Catalyst durability

Measurement of Local Impedance Characteristics of In-Plane PEM Electrolyzer Component Features via Segmented Cell

Segmented cells are a class of advanced diagnostic devices that enable the measurement of current distribution within the active area of an electrochemical cell, allowing for the evaluation of localized impacts from operating conditions, flow fields and component inhomogeneities. Segmented cell devices have been applied to support R&D efforts for the advancement of polymer electrolyte membrane fuel cell technologies and more recently proton exchange membrane water electrolysis (PEMWE). Beyond current density distributions, segmented cells have been successfully deployed to collect the distribution of other relevant parameters such as high frequency resistance and electrode potentials. Very recently, a promising impedance method has been reported for water electrolysis where a one-dimensional segmented cell is coupled to a multichannel potentiostat, to enable the measurement of local cell impedances, further expanding the diagnostic capabilities of the segmented cell. In this study, we will present recent efforts to accurately measure local impedance characteristics for a PEMWE cell using a two-dimensional segmented cell device coupled with a multichannel potentiostat. The distribution of local resistances, i.e. high frequency, charge transfer, mass transport and catalyst layer, and iR-free overpotentials were successfully measured after eliminating sources of random and systematic error. We will discuss the application of this diagnostic on a cell containing a 1 cm feature simulating an ionomer skin. The results from these tests give insights if such an irregularity needs to be classified as a defect, and highlight the usefulness of coupling impedance spectroscopy with segmented cells for holistic spatial diagnostics of electrochemical devices.

08 HYDROGEN

PFSA-Ionomer Adsorption to C and Pt/C Particles in Fuel-Cell Inks

Catalyst inks used to make fuel-cell electrodes consist of Pt/C catalyst particles and a perfluorosulfonic acid (PFSA) ionomer dispersed in water/alcohol solvent mixtures. PFSA ionomer in the ink adsorbs to the surface of the catalyst particles, dictating the dispersion colloid properties. Following adsorption, the subsequent distribution of excess nonadsorbed ionomer in the ink then governs the final structure of the electrode. Here, we characterize the adsorption of the PFSA ionomer onto Pt/C catalyst particles. PFSA adsorption is largely irreversible. Adsorbed sulfonic-acid moieties impart a negative charge on the catalyst surface, causing electrostatic repulsion between the free ionomer in solution and the ionomer-covered Pt/C particle surface. The amount of adsorption is limited by the resulting electrostatic charge that grows as more ionomer adsorbs, and the catalyst surface becomes more negatively charged. Attenuating electrostatic repulsion by increasing the ink ionic strength promotes ionomer adsorption. Electrostatically limited adsorption is observed, irrespective of the solvent water/n-propanol ratio or the catalyst particle porosity and Pt loading. Experimentally measured ionomer adsorption isotherms are well predicted by a Smoluchowski-based kinetic adsorption model, in which the electrostatic energy barrier for adsorption is predicted from DLVO theory. These findings help to unravel the complex phenomena within these colloidal dispersions, allowing for subsequent tailoring of inks to optimize fuel-cell electrode structure and performance.

Adsorption

Confocal Raman Microscopy as an In Situ Probe of Volume Change in Hydration-Sensitive Polymer Membranes

An approach is described for measuring hydration-induced volume change within ion conductive polymer membranes and thin films by adapting the technique of confocal Raman microscopy. With careful consideration of factors that affect excitation and scattering within the confocal probe volume region, material swelling and deswelling were estimated from the intensities of polymer matrix spectral features. A high numerical aperture oil-immersion objective was used to achieve tight focusing within samples and the efficient collection of Raman scattered light. The approach is demonstrated for a fluorinated cation-exchange ionomer (Nafion) and the hydrocarbon anion-exchange ionomer Sustainion. Samples were monitored while under a nitrogen atmosphere that was cycled between dry and humid (∼50% relative humidity, RH) states. The volume changes estimated from the Raman spectra were in close agreement with those derived from conventional measurements. The reported work advances understanding needed to adapt confocal Raman microscopy for quantitative in situ and operando studies of ionomers within electrochemical devices, such as polymer electrolyte membrane fuel cells and electrolyzers, and lays a foundation for broader applications in the study of hydration-induced polymer swelling and the associated molecular level water and polymer framework structural changes.

Absorption

Synthesis of highly sulfonated 2,6-diphenyl-p-Phenylene oxide: A highly conductive membrane

Highly sulfonated aromatic polymers are desired for the possible highest performance of polymer electrolytes in fuel cells and electrolyzer applications. Here, we reported the method to prepare highly sulfonated 2,6-diphenyl-p-phenylene oxide (SP3O), a commercially available aromatic polymer, with the highest IEC of 4.42 meq/g. Three sulfonation reagents including chlorosulfonic acid (HSO3Cl), concentrated sulfuric acid (conc. H2SO4), and trimethylsilyl chlorosulfonate (TMSCS) were investigated for single and two-step sulfonation reactions. In addition, DMSO-assisted thermal crosslinking method was applied to prepare crosslinked SP3O membranes to improve their mechanical strength and film-forming ability. Proton exchange membrane from crosslinked SP3O displayed a proton conductivity as high as 250 mS/cm at 95 % RH and 60 °C.

Khomein, Piyachai

A New Electrode Paradigm Enabled by Co-Axial Electrospinning

A conventional electrode in a polymer electrolyte membrane fuel cell (PEMFC) often imposes competing requirements on the ionomer, which must enable efficient proton conduction while allowing sufficient oxygen transport. To address these material-level requirements, a co-axial electrospun electrode comprising of a pristine ionomer core and a multifunctional platinum-carbon-ionomer shell is introduced. By decoupling proton and oxygen transport pathways, this architecture enables independent tailoring of core and shell chemistries and their interfaces. The core-shell structure of the electrospun fibers is confirmed by microscopy, while electrochemical and transport properties are quantified using electrochemical impedance spectroscopy and limiting-current diagnostics. The co-axial fibers in their current version meet or exceed the performance of conventional ultrasonically sprayed electrode at relative humidities above 75%, enabled by improvements in non-Fickian diffusion processes. This work establishes co-axial electrospun electrodes as a versatile platform for advanced PEMFC electrodes and a wide range of electrochemical applications, including CO2 electrolysis, water electrolysis, and critical mineral separations.

08 HYDROGEN