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At least 487 records · Page 27

Biaxial Strains Mediated Oxygen Reduction Electrocatalysis on Fenton Reaction Resistant L1 0 ‐PtZn Fuel Cell Cathode

Abstract PtM alloy catalysts (e.g., PtFe, PtCo), especially in an intermetallic L1 0 structure, have attracted considerable interest due to their respectable activity and stability for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, metal‐catalyzed formation of ·OH from H 2 O 2 (i.e., Fenton reaction) by Fe‐ or Co‐containing catalysts causes severe degradation of PEM/catalyst layers, hindering the prospects of commercial applications. Zinc is known as an antioxidant in Fenton reaction, but is rarely alloyed with Pt owing to its relatively negative redox potential. Here, sub‐4 nm intermetallic L1 0 ‐PtZn nanoparticles (NPs) are synthesized as high‐performance PEMFC cathode catalysts. In PEMFC tests, the L1 0 ‐PtZn cathode achieves outstanding activity (0.52 A mg Pt −1 at 0.9 V iR ‐free , and peak power density of 2.00 W cm −2 ) and stability (only 16.6% loss in mass activity after 30 000 voltage cycles), exceeding the U.S. DOE 2020 targets and most of the reported ORR catalysts. Density function theory calculations reveal that biaxial strains developed upon the disorder‐order (A1L1 0 ) transition of PtZn NPs would modulate the surface PtPt distances and optimize PtO binding for ORR activity enhancement, while the increased vacancy formation energy of Zn atoms in an ordered structure accounts for the improved stability.

Liang, Jiashun↗

Toward Optimizing Electrospun Nanofiber Fuel Cell Catalyst Layers: Microstructure and Pt Accessibility

This work investigates how local ionomer/platinum (Pt) interactions and ionomer distribution in electrospun Pt/Vulcan nanofiber electrodes impact ionomer coverage, proton accessibility, and oxygen reduction reaction (ORR) performance in proton-exchange membrane fuel cells. Insights from various in situ electrochemical diagnostics were utilized in conjunction with ex situ microscopic characterization to understand how the electrode microstructure—both at the aggregate level and near the ionomer/platinum interface—is affected by electrospinning in comparison to ultrasonic spraying. The effect of the carrier polymer poly(acrylic acid) (PAA) concentration from 5–20 wt % (with respect to total ink solids) on the resulting nanofiber morphology is discussed. Electron microscopy observations and CO displacement measurements indicated that Pt/Vulcan nanofibers prepared with a higher PAA concentration (15 wt %) were conformally coated with a film of ionomer on the exterior of the fiber, which resulted in an overall lower ionomer coverage on both Pt and carbon throughout the fiber diameter. In contrast, 10 wt % PAA leads to a uniform intrafiber distribution of the ionomer within the fibers, increasing the overall ionomer coverage and proton accessibility under both wet and dry conditions. These differences in the local ionomer coverage on Pt between 10 and 15 wt % PAA were also attributed to differences in the adsorption/interaction affinities between PAA and the ionomer onto the catalyst surface in the ink using zeta potential measurements. Additional fuel cell electrochemical tests on the electrospun electrodes show improvements in ORR kinetics and high-current-density H 2 /air performance compared to the ultrasonically sprayed electrodes.

25 ENERGY STORAGE↗

Electrochemical Evolution of Fuel Cell Platinum Nanocatalysts on Carbon Nanotubes at the Atomic Scale

The evolution of Pt nanoparticles supported on carbon nanotubes is analyzed before and after electrochemical potential cycling, using identical location aberration-corrected transmission electron microscopy, for applications in proton exchange membrane fuel cells. The work is focused on the half-cell accelerated stress test protocol of potential cycles ranging between 1.0 and 1.5 V RHE to represent the start-up/shutdown settings of a fuel cell vehicle. The research work reveals that particle migration and coalescence are key mechanisms for a reduction in the Pt nanoparticle surface area at the early stages of potential cycling. Further, the mechanism for particle movement and coalescence is attributed to carbon corrosion, catalyzed either by Pt or by bulk corrosion of the carbon nanotubes. Carbon corrosion results in the appearance of carbon vacancies at the carbon nanotube/Pt nanoparticle interface during cycling, as well as the formation of edge and surface defects. During cycling, the concentration of the dissoluble Pt increases. As soon as a significant amount is reached, subnanometer/atomic clusters emerge on the carbon nanotube support, which can move and coalesce, or redeposit on the surface of larger particles through Ostwald ripening.

25 ENERGY STORAGE↗

Fuel Cell Stack Model for Real-Time Simulation of Grid-Connected Applications

Fuel cell stacks coupled with electrolyzers and hydrogen storage sites can be a promising category of distributed energy resources for both grid-connected and stand-alone power systems. However, because of high costs, at-scale hardware testing of fuel cell stacks for grid-connected applications is not economically viable at present. A model-based system that can accurately captures the steady-state and dynamic response of fuel cell stacks over long time periods (hours), is needed. This paper demonstrate a real-time electromagnetic transient model of a megawatt-scale, grid-connected proton exchange membrane fuel cell stack, coupled with a mass-based hydrogen storage system. This model can emulate the electrical steady-state and dynamic response of grid-connected fuel cell stacks. We validate the model using the response of commercial hardware fuel cell stacks and analytical models in the literature - using a digital real-time simulator (RSCAD). The proposed real-time model is then used to simulate cases spanning different time horizons and to design controller-hardware-in-the-loop experiments to evaluate controllers for hydrogen stations.

activation potential↗

Discovering Reactant Supply Pathways at Electrode/PEM Reaction Interfaces Via a Tailored Interface-Visible Characterization Cell

In situ and micro-scale visualization of electrochemical reactions and multiphase transports on the interface of porous transport electrode (PTE) materials and solid polymer electrolyte (SPE) has been one of the greatest challenges for electrochemical energy conversion devices, such as proton exchange membrane electrolyzer cells (PEMECs), CO 2 reduction electrolyzers, PEM fuel cells, etc. Here, an interface-visible characterization cell (IV-CC) is developed to in situ visualize micro-scaled and rapid electrochemical reactions and transports in PTE/SPE interfaces. Taking the PEMEC of a green hydrogen generator as a study case, the unanticipated local gas blockage, micro water droplets, and their evolution processes are successfully visualized on PTE/PEM interfaces in a practical PEMEC device, indicating the existence of unconventional reactant supply pathways in PEMs. Further comprehensive results reveal that PEM water supplies to reaction interfaces are significantly impacted with current densities. Here these results provide critical insights about the reaction interface optimization and mass transport enhancement in various electrochemical energy conversion devices.

30 DIRECT ENERGY CONVERSION↗

Surface Functionalization of Carbon Black for PEM Fuel Cell Electrodes

Abstract Carbon‐based materials are extensively used in fuel cell applications due to their crucial role in maintaining high performance. Particularly, carbon black (CB) stands out as a preferred electrode material for fuel cells, owing to its high electrical conductivity and large surface area. This review focuses on the functionalization of CB and its use as a support for Pt‐based catalysts in proton exchange membrane fuel cells. Functionalization strategies include oxidation, covalent functionalization, as well as polymer grafting or impregnation. Various approaches to functionalize the CB surface are discussed that effectively tailor the surface properties of electrodes, leading to improved fuel cell performance. The improvements are seen in enhanced dispersibility of catalyst particles, better ionomer distribution, increased catalyst stability, and reduced carbon corrosion. This review provides an overview of various modifications applied to CB to enhance their structural and electrochemical properties, thereby boosting fuel cell performance.

74 ATOMIC AND MOLECULAR PHYSICS↗

Electrospun Hybrid Perfluorosulfonic Acid/Sulfonated Silica Composite Membranes

Electrospinning was employed to fabricate composite membranes containing perfluorosulfonic acid (PFSA) ionomer, poly(vinylidene fluoride) (PVDF) reinforcement and a sulfonated silica network, where the latter was incorporated either in the PFSA matrix or in the PVDF fibers. The best membrane, in terms of proton conductivity, was made by incorporating the sulfonated silica network in PFSA fibers (Type-A) while the lowest conductivity membrane was obtained when sulfonated silica was incorporated into the reinforcing PVDF fibers (Type-B). A Type-A membrane containing 65 wt.% PFSA with an embedded sulfonated silica network (at 15 wt.%) and with 20 wt.% PVDF reinforcing fibers proved superior to the pristine PFSA membrane in terms of both the proton conductivity in the 30–90% RH at 80 °C (a 25–35% increase) and lateral swelling (a 68% reduction). In addition, it was demonstrated that a Type-A membrane was superior to that of a neat 660 EW perfluoroimide acid (PFIA, from 3M Co.) films with respect to swelling and mechanical strength, while having a similar proton conductivity vs. relative humidity profile. This study demonstrates that an electrospun nanofiber composite membrane with a sulfonated silica network added to moderately low EW PFSA fibers is a viable alternative to an ultra-low EW fluorinated ionomer PEM, in terms of properties relevant to fuel cell applications.

36 MATERIALS SCIENCE↗

A harmonized protocol to assess the single-cell performance of proton exchange membrane water electrolyzers

The harmonization of testing protocols for proton exchange membrane (PEM) electrolyzers is essential for ensuring accurate and reliable performance assessments and accelerating the development of hydrogen production technologies. This protocol provides a structured approach to PEM electrolyzer setup and testing, incorporating key considerations for test station design and single-cell characterization techniques. Polarization curves and electrochemical impedance spectroscopy (EIS) are detailed, along with best practices from academic and industry research groups to enhance data accuracy and comparability. By addressing material variability and harmonizing testing methodologies, this framework enables more precise evaluations of membrane electrode assemblies and electrolyzer components. Harmonized protocols not only streamline development efforts but also foster collaboration across institutions, ultimately supporting the commercialization of hydrogen solutions through improved stack efficiency and durability.

08 HYDROGEN↗

Revealing the Crystalline Architecture of Semicrystalline Ion Exchange Membranes for the Design of Conductive and Durable Alkaline Anion Exchange Membranes

Alkaline anion exchange membrane (AAEM) fuel cells offer a cost-effective alternative to proton exchange membrane (PEM) fuel cells by eliminating the need for expensive precious metal catalysts. In both PEMs and AAEMs, semicrystalline polymers are a common choice, as the crystalline domains can act as mechanical reinforcements that limit swelling and promote mechanical durability in the material. However, spatially resolved characterization of crystalline organization in ion exchange membranes beyond ensemble-averaged X-ray scattering is underrepresented, likely in part due to ionization damage limitations in soft materials. Here, in this study, we resolve the nanometer-size crystallites in semicrystalline ion exchange membranes by applying cryogenic four-dimensional scanning transmission electron microscopy (cryo-4D-STEM) along with data-processing algorithms designed to optimize signals at a low dose to minimize radiation damage. We investigate the effects of synthesis components, including molecular weight and thermal treatment, on a model system of AAEMs in comparison to Nafion, the most commonly used and commercially successful PEM today. We find that excess water uptake in polymer membranes, a property directly associated with weak mechanical durability and with possible negative impacts on ion conductivity, can be reduced by over 30% by varying the polymer's crystalline morphology through changes in synthesis parameters such as molecular weight and thermal history. Our results indicate that this improvement is correlated with smaller crystalline domains with a more homogeneous distribution. More broadly, these results demonstrate how the crystalline architecture of polymer membranes can be tuned through their chemistry and thermal treatment in order to improve their conductivity and durability for commercial fuel cell performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically Grown Ultrathin Platinum Nanosheet Electrodes with Ultralow Loadings for Energy-Saving and Industrial-Level Hydrogen Evolution

Nanostructured catalyst-integrated electrodes with remarkably reduced catalyst loadings, high catalyst utilization and facile fabrication are urgently needed to enable cost-effective, green hydrogen production via proton exchange membrane electrolyzer cells (PEMECs). Herein, benefitting from a thin seeding layer, bottom-up grown ultrathin Pt nanosheets (Pt-NSs) were first deposited on thin Ti substrates for PEMECs via a fast, template- and surfactant-free electrochemical growth process at room temperature, showing highly uniform Pt surface coverage with ultralow loadings and vertically well-aligned nanosheet morphologies. Combined with an anode-only Nafion 117 catalyst-coated membrane (CCM), the Pt-NS electrode with an ultralow loading of 0.015 mg Pt cm -2 demonstrates superior cell performance to the commercial CCM (3.0 mg Pt cm -2 ), achieving 99.5% catalyst savings and more than 237-fold higher catalyst utilization. The remarkable performance with high catalyst utilization is mainly due to the vertically well-aligned ultrathin nanosheets with good surface coverage exposing abundant active sites for the electrochemical reaction. Overall, this study not only paves a new way for optimizing the catalyst uniformity and surface coverage with ultralow loadings but also provides new insights into nanostructured electrode design and facile fabrication for highly efficient and low-cost PEMECs and other energy storage/conversion devices.

42 ENGINEERING↗

Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells

We report that state-of-the-art automotive fuel cells that operate at about 80 °C require large radiators and air intakes to avoid overheating. High-temperature fuel cells that operate above 100 °C under anhydrous conditions provide an ideal solution for heat rejection in heavy-duty vehicle applications. Here we report protonated phosphonic acid electrodes that remarkably improve the performance of high-temperature polymer electrolyte membrane fuel cells. The protonated phosphonic acids comprise tetrafluorostyrene-phosphonic acid and perfluorosulfonic acid polymers, where a perfluorosulfonic acid proton is transferred to the phosphonic acid to enhance the anhydrous proton conduction of fuel cell electrodes. By using this material in fuel cell electrodes, we obtained a fuel cell exhibiting a rated power density of 780 mW cm -2 at 160 °C, with minimal degradation during 2,500 h of operation and 700 thermal cycles from 40 to 160 °C under load.

25 ENERGY STORAGE↗

Electrochemical devices and fuel cell systems

Electrochemical devices including electrochemical pumps (ECPs) and fuel cell systems comprising a fuel cell and an ECP are disclosed. In particular, this electrochemical device can be an ECP that comprises an anode, a cathode and an anion exchange polymer separating the anode from the cathode. The ECP can be coupled to a hydroxide exchange membrane fuel cell (HEMFC) that is disclosed herein as a fuel cell system. These devices can be used in methods for removing carbon dioxide from air and for generating electricity.

Yan, Yushan↗

Electrochemical devices and fuel cell systems

Electrochemical devices including electrochemical pumps (ECPs) and fuel cell systems comprising a fuel cell and an ECP are disclosed. In particular, this electrochemical device can be an ECP that comprises an anode, a cathode and an anion exchange polymer separating the anode from the cathode. The ECP can be coupled to a hydroxide exchange membrane fuel cell (HEMFC) that is disclosed herein as a fuel cell system. These devices can be used in methods for removing carbon dioxide from air and for generating electricity.

Yan, Yushan↗

Effects of Ink Formulation on the Structure and Performance of PGM-Free Catalyst Layer in PEMFCs

Platinum group metal (PGM) catalysts are the major electrocatalysts for oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cells (PEMFCs). The cost becomes unaffordable if the PEMFC is in massive application. The PGM-Free catalyst shows very promising activity in rotation disk electrode (RDE) testing. The half-wave potential could reach 0.91 V versus standard hydrogen electrode (SHE). However, in a membrane electrode assembly (MEA), the performance of PGM-Free catalysts is not good enough to replace the PGM catalysts. Since the PGM-free catalysts are so different from the PGM catalysts in terms of catalytic activity, stability, surface conditions, particle size, etc., the fabrication of PGM-Free catalyst MEA cannot simply copy the method of making PGM MEA. Here we proposed a novel method of fabricating PGM-Free catalyst MEA, so that the intrinsic catalyst activity from RDE can be translated into MEA performance. The method is based on the catalyst coated membrane (CCM) method using optimized ionomer to carbon (I/C) ratio and solvent mixture of catalyst ink. Using this method, the PGM-free catalyst MEA achieved the current density 44.9 mA cm -2 at 0.9 V iR-free in H 2 /O 2 and 150 mA cm -2 at 0.8 V in H 2 /air, which surpassed the performance targets of US Department of Energy (DOE)for PGM-Free catalyst MEA. The property (solvent composition, dispersion of catalyst and ionomer in an ink), structure (pore structure) and the MEA performance have been characterized using, mercury intrusion porosimetry (MIP), MEA testing. A property-structure-performance relationship has been established.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crack detection in fuel cell electrodes using a spatial filtering technique for overcoming noisy backgrounds

Image processing is a powerful tool that allows for rapid and automated data parsing in settings that occupy large variable spaces and require large data sets. Feature detection on difficultly discerned backgrounds is a subset of image processing that facilitates the extraction of quantitative metrics from otherwise subjective data. Crack detection and quantification is an important capability in polymer electrolyte membrane fuel cell quality control, failure analysis, and optimization. This work presents a technique to perform crack detection and quantification which overcomes challenges faced by commonly used image segmentation techniques. We demonstrate the use of a geometrically filtered noise‐level detection technique to select a binary threshold value from which we then quantify how cracked a sample is. Furthermore, we demonstrate the accuracy of our technique using programmatically generated test images of known crack amounts and their performance on real‐world fuel cell catalyst layer samples.

30 DIRECT ENERGY CONVERSION↗

Phosphoric Acid-Doped Ion-Pair Coordinated PEMs with Broad Relative Humidity Tolerance

Proton exchange membrane (PEM) capable of working over a broad operating condition window is critical for successful adoption of PEM-based electrochemical devices. In this work, phosphoric acid (PA)-doped biphenyl-backbone ion-pair coordinated PEMs were prepared by quaternization of BPBr-100, a precursor polymer, with three different tertiary amines including trimethylamine, 1-methylpiperidine, and 1,2-dimethylimidazole followed by membrane casting, ion exchange reaction to hydroxide ion, and doping with PA. The resulting PA-doped ion-pair PEMs were characterized in terms of PA doping level, proton conductivity, relative humidity (RH) tolerance, thermal stability, and mechanical properties. PA doping levels were between six and eight according to acid-base titration. The size and structure of the cation group of ion-pair polymers were found to affect the PA doping level and water uptake. Proton conductivity was studied as a function of RH over a wide range of 5% to 95% RH. Stable conductivity at 80 °C was observed up to 70% RH for 10 h. Mechanical property characterization indicates that the PA doping process resulted in more ductile membranes with significantly increased elongation at break due to the plasticization effect of PA. A combination of high proton conductivity at low RH conditions, and good humidity tolerance makes this new class of PEMs great potential candidates for use in electrochemical devices such as proton exchange membrane fuel cells and electrochemical hydrogen compressors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biomimetic Fe–Cu Porphyrrole Aerogel Electrocatalyst for Oxygen Reduction Reaction

The development of bioinspired catalysts for oxygen reduction reaction is one of the most prominent pathways in the search for active materials to replace Pt-based catalysts in fuel cells. Herein, we report innovative bioinspired catalysts using a directed synthetic pathway to create adjacent Cu and Fe sites. This catalyst is composed of a covalent 3D framework in an aerogel form. Aerogels are high surface area and porous hierarchical structures that can allow the formation of ultrahigh active site density and optimized mass transport of reactants and products to and from the catalytic sites. The aerogel-based catalyst exhibits high performance in a half-cell in 0.1 M KOH, with an onset potential of 0.94 V vs RHE and half-wave potential of E 1/2 = 0.80 V vs RHE, high selectivity toward the four-electron reduction of oxygen to hydroxide anions, and high durability. These results are well-translated to the anion exchange membrane fuel cell (AEMFC), reaching an open circuit potential of 0.97 V and iR-corrected peak power density of 0.51 W cm –2 . Based on density functional theory calculations, the improved activity relative to the Fe-porphyrin and Cu-corrole is ascribed to the effect of the extended carbon network and the proximity of the metal sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗