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DOE OSTI2020

Use of a segmented cell for the combinatorial development of platinum group metal-free electrodes for polymer electrolyte fuel cells

The development of novel platinum group metal (PGM)-free catalysts is a difficult task, particularly when coupled with the integration into a cathode catalyst layer (CCL). The optimization of such PGM-free electrode structures is often non-linear and iterative, making it a demanding task due to the high number of parameters that affect performance. To accelerate both materials discovery and electrode development, this work demonstrates the application of a high-resolution segmented cell (SC) with 121 segments of 0.413 cm 2 size for combinatorial high-throughput PGM-free catalyst screening and CCL optimization. The approach utilizes three flow-field strips with active areas of 4.45 cm 2 each, distributed over 11 segments. Electrodes with identical catalyst material and fabrication method result in reproducible data with typically less than 10% variation between each segment and match in performance with differential single cell data. High throughput testing of combinatorial sample sets, with varied PGM-free electrocatalyst materials or electrode composition, demonstrated the ability to rapidly discern high performing outliers, and establish or confirm trends in electrode optimization. The results indicated significant performance benefits of electrodes with ionomer content of 45 wt% over lower values, and of water rich inks with 82% water content over those with 50%.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2024

A Three–Dimensional Nanoscale View of Electrocatalyst Degradation in Hydrogen Fuel Cells

The loss of platinum (Pt) electrochemically active surface area (ECSA) is a critical degradation mode that often becomes a limiting factor for heavy-duty proton exchange membrane fuel cell vehicles. High surface area carbon supports have been shown to improve Pt dispersion and limit detrimental ionomer-electrocatalyst interactions due to their large interior pore volume. Here, in this work, using automated scanning transmission electron tomography, the degradation of nanoparticles located on the interior versus exterior surfaces of the carbon support is compared following a catalyst-specific accelerated stress test (AST) of 90,000 voltage cycles between 0.6 V to 0.95 V. The results reveal a notable increase in median particle size for both interior and exterior Pt catalyst particles, with a slightly higher increase in particle size distribution and loss of specific surface area for the particles located on the exterior carbon surface. The fraction of Pt nanoparticles that reside within the interior of the carbon support also increased following the AST test, accompanied by evidence of an increase in average carbon mesopore size. Here, the results shed light on the degradation mechanisms affecting electrochemical properties and the enhanced particle accessibility at lower relative humidity.

08 HYDROGEN↗

DOE OSTI2021

Effects of Ionic Group Distribution on the Structure and Dynamics of Amorphous Polymer Melts

Ionizable groups tethered to a polymer backbone often associate to form ionic clusters, whose features are determined by the balance of the polymer backbone and electrostatics. These assemblies impact the dynamics of the macromolecules and their ability to transport ions. Here, using fully atomistic molecular dynamics (MD) simulations, we investigate the effects of the distribution of ionizable groups along the polymer backbone on cluster characteristics and the resulting impacts on the structure and dynamics of amorphous polymers. Particularly, we probe polystyrene sulfonates (PSS) with random, precise, and block configurations of the SO 3 – sulfonate groups along the backbone with Na + as the counterion. We find that the distribution of the ionic groups affects the shape and distribution of the clusters as well as the internal packing of the ionizable groups in the cluster and the number of unique chains that participate in each cluster, affecting the structure and the dynamics of the polymers. Furthermore, the signature of ionic clusters, observed in the static structure factor S(q) for all three distributions, is significantly more pronounced for the precise and blocky polymers compared to the random one. Remarkably, we find that the local mobility of the polymer segments is not only affected by the number and size of the clusters but also by the number of polymer chains associated with clusters.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Clustering Effects on the Structure of Ionomer Solutions: A Combined SANS and Simulations Study

Ionic assemblies, or clusters, determine the structure and dynamics of ionizable polymers and enable their many applications. Fundamental to attaining well-defined materials is controlling the balance between van der Waals interactions that govern the backbone behavior and the forces that drive the formation of ionic clusters. Here, using small angle neutron scattering and fully atomistic molecular dynamics simulations, the structure of a model ionomer, sulfonated polystyrene in toluene solutions, was investigated as the cluster cohesion was tweaked by the addition of ethanol. The static structure factor was measured by both techniques and correlated with the size of the ionic clusters as the polymer concentration was varied. The conjunction of SANS results and molecular insight from MD simulations enabled the determination of the structure in these inhomogeneous networks on multiple length scales. Additionally, we find that across the entire concentration range studied, a network driven by the formation of ionic clusters was formed, where the size of the clusters drives the inhomogeneity of these systems. Tweaking the ionic clusters through the addition of ethanol impacts the packing of the sulfonated groups, their shape, and their size distribution, which in turn, affects the structure of these networks.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Hybrid Ionomer-Free Porous Transport Electrodes With Catalyst Coated Membranes for Enhanced Water Electrolysis

To promote industrial uptake of clean hydrogen production technologies such as polymer electrolyte membrane (PEM) water electrolyzers, advancements in catalyst layer (CL) morphology are required. We demonstrate how improved electrochemical performance can be achieved when using an ionomer free porous transport electrode (PTE) coupled with a traditional catalyst coated membrane (CCM) assembly in PEM water electrolyzers. Notably, we reveal that the superior performance achieved when utilizing a hybrid PTE and CCM assembly is due to enhanced ohmic performance caused by optimal contact with both the porous transport layer (PTL) and PEM interfaces. Using operando neutron radiography, we demonstrate that configurations utilizing a CCM resulted in more rapid water replenishment to reaction sites, indicating enhanced membrane hydration beneficial for performance. This enhanced membrane hydration coupled with improved contact area at the PEM-catalyst layer (CL) and PTL-CL interfaces was revealed through the reduced ohmic overpotentials of the hybrid PTE-CCM design, which achieved the lowest ohmic overpotential of 431 mV at 2000 mA cm−2. While the average in-plane water distributions are generally similar between cell configurations, we reveal that utilizing a PTE configuration promotes a more homogenous water distribution near the CL-membrane interface due to enhanced catalyst utilization.

Seip, Tess [ORNL] (ORCID:0000000232740594)↗

DOE OSTI2024

Advanced Electrode Structures for Proton Exchange Membrane Fuel Cells: Current Status and Path Forward

Abstract Proton exchange membrane fuel cells (PEMFCs) have demonstrated their viability as a promising candidate for clean energy applications. However, performance of conventional PEMFC electrodes, especially the cathode electrode, suffers from low catalyst utilization and sluggish mass transport due to the randomly distributed components and tortuous transport pathways. Development of alternative architectures in which the electrode structure is controlled across a range of length scales provides a promising path toward overcoming these limitations. Here, we provide a comprehensive review of recent research and development of advanced electrode structures, organized by decreasing length-scale from the millimeter-scale to the nanometer-scale. Specifically, advanced electrode structures are categorized into five unique architectures for specific functions: (1) macro-patterned electrodes for enhanced macro-scale mass transport, (2) micro-patterned electrodes for enhanced micro-scale mass transport, (3) electrospun electrodes with fiber-based morphology for enhanced in-plane proton transport and through-plane O 2 transport, (4) enhanced-porosity electrodes for improved oxygen transport through selective inclusion of void space, and (5) catalyst film electrodes for elimination of carbon corrosion and ionomer poisoning. The PEMFC performance results achieved from each alternative electrode structure are presented and tabulated for comparison with conventional electrode architectures. Moreover, analysis of mechanisms by which new electrode structures can improve performance is presented and discussed. Finally, an overview of current limitations and future research needs is presented to guide the development of electrode structures for next generation PEMFCs. Graphical Abstract Development of improved electrode architectures with the control of structure on length scales ranging from millimeters to nanometers could enable a new generation of fuel cells with increased performance and reduced cost. This paper presents an in-depth review and critical analysis of recent developments and future outlook on the design of advanced electrode structures.

25 ENERGY STORAGE↗

DOE OSTI2023

Investigation of Nanoparticle Degradation in Hydrogen Fuel Cell Systems through Automated Electron Microscopy

Proton exchange membrane fuel cells (PEMFC) are promising devices for the deployment of hydrogen-powered heavy-duty vehicles, providing a higher efficiency for similar driving range and fueling time than the existing ones. However, PEMFCs still encounter durability challenges mainly due to catalyst degradation in the cathode. Mitigating these performance losses requires a better understanding of the degradation mechanisms under heavy-duty accelerated stress tests (ASTs) [1]. Scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) are key tools for the analysis of Pt and PtCo nanoparticle size, spatial distribution and composition [2]. Electron tomography is also used to determine the rate and type of degradation of catalyst nanoparticles as a function of their position on the carbon support. In this work, automated data acquisition software, paired with a custom Python code, have been used to study the effect of different accelerated stress tests (ASTs) on nanoparticle coarsening [2]. Figure 1 shows high-angle annular dark-field (HAADF)-STEM images and EDS maps comparing the cathodes of membrane electrode assemblies (MEAs) following an electrocatalyst AST performed under H2/N2 with that of the heavy-duty AST performed under H2/air. We will discuss how AST conditions affect considerably the spatial distribution of the nanoparticles across the electrode between the membrane and microporous layer. Although the median particle size increased more in the MEA aged under the heavy-duty AST, as determined using a high-throughput image analysis, the quantitative EDS measurements demonstrate that the electrocatalyst AST resulted in more Pt and Co dissolution from the cathode, which is another important indicator of electrocatalyst degradation. We will further present the impact of the relative humidity (% RH) on the degradation mechanisms demonstrated using the same approach. Electron tomography has been used to distinguish the Pt nanoparticles residing on the carbon support surface (exterior) from those within the pore structure (interior) in order to determine the relative stability of interior and exterior nanoparticles. As shown in Figure 2, we will compare the Pt catalyst particle size at the beginning of test (BOT) and end of test (EOT), and discuss the importance of automating the electron tomography workflow, i.e. acquisition, reconstruction, and visualization, to increase sampling and determine the standard deviation of these measurement. The outlook for utilizing low-dose cryo-tomography for limiting damage to the catalyst, support, and especially proton-conducting ionomer will also be discussed [3].

Amichi, Lynda↗

DOE OSTI2025

Anions in Corrosion: Influence of Polymer Electrolytes on the Interfacial Ion Transfer Kinetics of Cu at Au(111) Surfaces

The corrosion kinetics of metals in the presence of polymer electrolytes—which are often used in devices for the electrochemical production of hydrogen, hydrocarbons, and alcohols—is convoluted by transport and ill-defined reactive interfaces which mask the fundamental reaction kinetics. Underpotential-deposited monolayers of Cu at Au(111) surfaces provide a structurally welldefined active site for interfacial ion transfer, with a fixed number of sites available for adsorption. Here, we investigate the adsorption behavior of Cu at Au(111) surfaces across a series of sulfate and sulfonate electrolytes, to understand how anion structure influences the kinetics of elementary interfacial ion-transfer reactions. The influence of anion structure is most significant at high adsorbate coverage, with similar adsorption isotherms and kinetics observed for all three molecular sulfates and sulfonates. In contrast, a suspended perfluorosulfonic acid ionomer reduced both the equilibrium coverage of Cu as well as the standard exchange rate at Au(111) at low coverages of Cu. These results suggest that electrocatalyst corrosion is inhibited for metal nanoparticles supported at polymer electrolytes due to changes in adsorbate coverage as well as suppressed kinetics for interfacial ion transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Design of non-fluorinated proton exchange membranes from Poly(Terphenyl fluorenyl isatin) with fluorene-linked sulfonate groups and microblock structures

Proton exchange membranes (PEMs) are essential components in energy storage and conversion devices, such as fuel cells and electrolyzers. Here, in this study, we developed a series of non-fluorinated PEMs from poly(terphenyl fluorenyl isatin) with fluorene-pendent disulfonate groups. These polymers feature a microblock structure composed of hydrophobic blocks, hydrophilic blocks, and alternating blocks, arising from the differences in reactivity, concentration, and solubility between the hydrophobic p-terphenyl and hydrophilic disulfonated fluorene monomers. As a result, the sulfonic acid groups are unevenly distributed along the polymer chains, forming densely charged regions (IEC = 3.52 meq/g) with large ion clusters and lightly charged regions (IEC = 2.16 meq/g) with small ion clusters. This microstructure, combined with the degree of sulfonation, significantly influences the overall properties of the membranes, including robust mechanical strength (47.1–63.2 MPa), high thermal stability (up to 270 °C), low swelling ratio (18–25% at 80 °C), and high proton conductivity (136–169 mS/cm in deionized water at 80 °C). The PFLSH60 membrane demonstrated comparable fuel cell performance to Nafion 212. Its hydrogen crossover current density was more than two times lower (0.86 mA/cm 2 for PFLSH60 compared to 1.83 mA/cm 2 for Nafion 212) under testing conditions of 80 °C and 100% RH. This significantly reduced crossover improves fuel utilization in fuel cell stacks. This work offers valuable insights into the design of robust, high-performance PEMs by systematically analyzing the relationships between membrane structure, properties, and performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Mechanism-Informed Breakdown: Understanding Degradation by Controlling Voltage-Hold Patterns in Proton Exchange Membrane Water Electrolyzers

Low catalyst loadings pose challenges to performance stability in proton exchange membrane (PEM) water electrolysis over extended operation. To study the impact of degradation mechanisms and voltage loss rates, different stress tests are applied to membrane electrode assemblies. Potential cycling conditions were observed to induce higher degrees of iridium (Ir) oxide crystallization, ionomer degradation, and catalyst layer (CL) thinning, which likely contributed to higher kinetic loss rates. On the other hand, while Ir migrating into the PEM (Ir band) generally impairs performance, the interconnected and more uniform Ir band formed under a constant 2 V hold may allow for Ir at the catalyst/membrane interface to remain electronically connected and kinetically accessible, as well as indicate greater Ir site access during the applied stressor. The 2 V hold also demonstrates improved kinetic durability through a lower Tafel slope, faster polarization kinetics, and reduced charge transfer resistance. In contrast, potential cycling caused the migration of disconnected Ir agglomerates into the membrane bulk and created a steady increase in charge transfer resistance, a more dramatic decrease in capacitance (46.7% loss), and significant damage to the surrounding ionomer, indicating a decline in both the quality and quantity of active sites in the anode CL. This work underscores the distinct degradation pathways associated with load holds versus cycling, highlighting the role of catalyst-ionomer interactions in kinetic performance and long-term stability. These insights can inform operational strategies for PEM electrolyzers powered by intermittent energy sources, aiming to minimize efficiency losses over extended operation.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Proteomic Insights into Trichome Responses to Elevated Elemental Stress in Cation Exchanger (CAX) Mutants

Abstract Research on elemental distribution in plants is crucial for understanding nutrient uptake, environmental adaptation and optimizing agricultural practices for sustainable food production. Plant trichomes, with their self-contained structures and easy accessibility, offer a robust model system for investigating elemental repartitioning. Transport proteins, such as the four functional cation exchangers (CAXs) in Arabidopsis, are low-affinity, high-capacity transporters primarily located on the vacuole. Mutants in these transporters have been partially characterized, one of the phenotypes of the CAX1 mutant being altered with tolerance to low-oxygen conditions. A simple visual screen demonstrated trichome density and morphology in cax1, and quadruple CAX (cax1-4: qKO) mutants remained unaltered. Here, we used synchrotron X-ray fluorescence (SXRF) to show that trichomes in CAX-deficient lines accumulated high levels of chlorine, potassium, calcium and manganese. Proteomic analysis on isolated Arabidopsis trichomes showed changes in protein abundance in response to changes in element accumulation. The CAX mutants showed an increased abundance of plasma membrane ATPase and vacuolar H-pumping proteins, and proteins associated with water movement and endocytosis, while also showing changes in proteins associated with the regulation of plasmodesmata. These findings advance our understanding of the integration of CAX transport with elemental homeostasis within trichomes and shed light on how plants modulate protein abundance under conditions of altered elemental levels.

59 BASIC BIOLOGICAL SCIENCES↗