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At least 73 records · Page 4

Recent developments in Pt–Co catalysts for proton-exchange membrane fuel cells

Development of Pt-based oxygen reduction reaction catalysts with high efficiency and high durability is central to the application of proton-exchange membrane fuel cell systems. Pt–Co bimetallic catalysts have drawn extensive attention owing to their capability of delivering high performance and long lifetime for fuel cell applications including light-duty and heavy-duty vehicles. However, further improvements in durability and performance are needed to meet market requirements. To fully exploit the potential of Pt–Co catalysts, new insights into the relationship between catalyst properties and fuel cell performance and durability are needed, and more effective methods to tailor the features of Pt–Co catalysts need to be developed. This review provides a summary and perspective on recent efforts, including work on customizing the Pt shell and Pt:Co ratio, tailoring the crystal structure, and improving carbon support properties, with a particular emphasis on mechanisms leading to enhancement of mass activity, power density, and durability in membrane electrode assembly testing.

25 ENERGY STORAGE↗

Structure and Sulfur: Tuning the Viscoelastic and Surface Properties of Natural Keratin Fibers

Natural keratin fibers, such as wool, possess a complex hierarchical structure that governs their mechanical properties and surface energy. However, the extent to which these characteristics are influenced by combined contributions of structural variations (e.g., fiber diameter, intermediate filament (IF) packing) and chemical composition (e.g., disulfide bond density) remains poorly understood. In this study, we investigate wool fibers from five sheep breeds (Merino, Polwarth, Cheviot, Eider, and Devon) to elucidate how these factors influence viscoelasticity and surface interactions. Using a multimodal approach integrating interfacial and bulk characterization methods, including inverse gas chromatography (IGC), atomic force microscopy-infrared spectroscopy (AFM-IR), X-ray photoelectron spectroscopy (XPS), uniaxial tensile testing, and synchrotron small-angle X-ray scattering (SAXS), we show that the nanometer-thick 18-methyleicosanoic acid (18-MEA) layer is consistently present across all wool types and plays a key role in governing hydrophobicity and surface heterogeneity. A controlled isothermal treatment at 200 °C, designed to cleave disulfide bonds, results in a nearly 40% reduction in specific surface area across all fiber types, accompanied by a significant decrease in tensile strength and 80% reduction in elongation at break for Merino and Devon wool, but limited influence on the mechanical properties of Eider fibers. Furthermore, rate-dependent tensile testing within the elastic regime reveals distinct viscoelastic responses among the fiber types, suggesting that the sulfur-rich protein matrix surrounding IFs and its structure contribute actively to stress partitioning. Altogether, when combined with conclusions from SAXS measurements of IF spacing, our work offers compelling insights into the role of the keratin-associated protein (KAP) matrix in shaping wool fiber mechanics. Differences in mechanical behavior among wool types, despite similar IF spacing or sulfur content, highlight the importance of matrix composition and cross-linking density, suggesting that the molecular architecture of the KAP network may be a dominant factor in determining fiber performance.

X-ray scattering↗

Modeling Planar Electrodes and Zero–Gap Membrane Electrode Assemblies for CO 2 Electrolysis

Multiphysics modeling enables probing of conditions inside a CO 2 electrolyzer that are difficult to measure, such as local concentrations and pH, as well as rapid testing of possible design changes. A one-dimensional model for a zero-gap membrane electrode assembly (MEA) CO 2 electrolyzer was developed with the assumption that catalyst layers interact with the membrane ionomer such that the ionomer affects the underlying kinetics. The kinetics for bicarbonate reacting to form hydrogen are fit using a planar electrode model for silver with an ionomer coating. The MEA model results are validated against experimental studies for current density and product selectivity. Flooding of the cathode is modeled using saturation curves, and results show that blocked pores in the microporous layer play a significant role in limiting the mass transport at high potentials (>2.8 V). Sensitivity studies showed that CO Faradaic efficiency can be increased by decreasing catalyst layer thickness and porosity, and decreasing KHCO 3 concentration.

30 DIRECT ENERGY CONVERSION↗

Meas. K+ -Ar Total Inelastic Cross Section at ProtoDUNE-SP

ProtoDUNE-SP is a single-phase liquid argon time projection chamber that took hadron test beam data in 2018. The test beam included positively charged kaons with test beam momenta of 6 GeV/c and 7 GeV/c, providing a sample to study kaons to benefit future DUNE proton decay and neutrino interaction studies with kaons in the final state. The total inelastic cross section of a positively charged kaon was measured at these test beam settings using the LArIAT thin-slice method of dividing the wires of the time projection chamber into target slices for calculating the cross section, which leverages the monolithic quality of liquid argon detectors. A Bayesian-like unfolding method using RooUnfold was applied to both the incident and interacting slice distributions to measure the cross sections at both test beam momenta. The talk will discuss the method of unfolding, optimization studies for unfolding, and applying systematic uncertainties using a LArIAT-style hadronic cross section using unfolding to extract a kaon total inelastic cross section.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Nanoporous Iridium Nanosheets for Polymer Electrolyte Membrane Electrolysis

The growth of the hydrogen economy is predicated on advancements in electrochemical energy technologies, with water electrolysis as a key component to the technological portfolio. Much of the focus on anode catalyst development for polymer electrolyte membrane water electrolyzers (PEMWE) is centered on activity as controlled by compositional and morphological impacts on reactant/intermediate/product adsorption. However, the effectiveness of this strategy is found to be limited upon integration of these materials into PEMWE membrane electrode assemblies (MEA). Regardless of catalyst activity, the combination of electrode inhomogeneity, ionomer integration, and high density of oxide-oxide interfaces yields significant performance losses associated with poor catalytic electrode conductivity. Here many of these limitations are addressed through the development of a unique catalyst morphology composed of nanoporous Ir nanosheets (npIr(x)-NS) that exhibit high catalytic activity for the anodic oxygen evolution reaction and superior electrode electronic conductivity in comparison to a commercial IrO2 nanoparticle catalyst. The utility of the npIr(x)-NS is demonstrated through incorporation into PEMWE MEAs where their performance exceeds that of commercial catalyst coated membranes at loadings as low as 0.06 mg(Ir) cm(-2) while exhibiting a negligible loss in performance following 50 000 accelerated stress test cycles.

Polymer Electrolyte Membrane Electrolysis↗

Mapping of Heterogeneous Catalyst Degradation in Polymer Electrolyte Fuel Cells

Pt catalysts in polymer electrolyte fuel cells degrade heterogeneously as the catalyst particles are exposed to local variations throughout the catalyst layer during operation. State-of-the-art analytical techniques for studying degradation of Pt catalysts do not possess fine spatial resolution to elucidate such non-uniform degradation behavior at a large electrode level. A new methodology is developed to spatially resolve and quantify the heterogeneous Pt catalyst degradation over a large area (several cm ) of aged MEAs based on synchrotron X-ray microdiffraction. PEFC single cells are aged using voltage cycling as an accelerated stress test and the degradation heterogeneity at a micrometer length scale is visualized by mapping Pt catalyst particle size after voltage cycling. It is demonstrated in detail that the Pt catalyst particle size growth is non-uniform and follows the flow field geometry. The Pt particle size growth is greater in the area under the flow field land, while it is minimal in the area under the flow field channel. Additional non-uniformity is observed with the Pt particle size increasing more rapidly at the air outlet area than the Pt particle size at the inlet area.

36 MATERIALS SCIENCE↗

Probing Electrode Transformation under Dynamic Operation for Alkaline Water Electrolysis

Alkaline water electrolyzers (AWEs) play a pivotal role in the realm of large-scale hydrogen production. However, AWEs face significant challenges in electrode degradation particularly under dynamic operating conditions, induced by reverse current phenomenon during frequent startup/shutdown. Herein, this study aims to rationalize the degradation mechanisms of AWEs under these conditions. A three-electrode membrane electrode assembly (MEA) setup is first utilized to decouple polarization behaviors of anode and cathode in AWEs. Following a proposed accelerated stress testing protocol, the setup allows for tracking individual electrode performance transformations during frequent reverse current operation. Integrating operando cell studies with in situ and post-mortem characterizations, it is showed that continuous formation of highly active species, nickel (oxy)hydroxides, improves the anode performance for oxygen evolution reaction. On the contrary, irreversible oxidation of nickel to β-nickel hydroxide results in a severe degradation of cathode, leading to material dissolution, poor electrical conductivity and loss of catalytic activity for hydrogen evolution reaction. These results provide insights in nickel-based electrode transformation mechanisms for alkaline water electrolysis and indicate that cathode with higher redox reversibility can potentially improve durability of AWEs under dynamic conditions.

08 HYDROGEN↗

ElectroCat: Platinum-Group-Metal-Free Engineered Framework Nano-Structure Catalyst (Final Technical Report)

Traditional synthesis methodologies that produce durable, highly active PGM-free electrocatalysts typically consist of a top-down approach utilizing a nitrogen-coordinating precursor, a metal precursor, and a support material. Nitrogen-coordinated transition metal complexes typically are absorbed onto a support material, which is then activated via high-temperature pyrolysis. Selection of the support and the nitrogen coordinating precursor has long been the focal point of efforts to maximize the number of accessible, catalytically active sites. In this project, GWE in collaboration with SRNL and NU will develop durable, highly active, low-cost, PGM-free electrocatalysts for polymer electrolyte membrane fuel cells designed and synthesized using a unique, bottom-up, rationally designed approach. Electrocatalysts are produced via polymerization reaction followed by a high-temperature pyrolysis step. Additionally, this project focuses on catalyst site and ORR mechanistic modeling to better understand the structure-property relationship.

08 HYDROGEN↗

CalTestBed - EvolOH - Testing of Hydroxide Exchange Membrane Water Electrolyzers and their Components (CRADA Final Report)

EvolOH is a Hydroxide Exchange Membrane Water Electrolyzer (HEMWE) company located in Menlo Park. LBNL helped EvolOH optimize MEA performance and durability through in/ex-situ materials characterization techniques. The finding of this project was used to develop an understanding of the performance limitations and component characterization toward commercializing HEMWE technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

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↗

Promoting Atomically Dispersed MnN 4 Sites via Sulfur Doping for Oxygen Reduction: Unveiling Intrinsic Activity and Degradation in Fuel Cells

Carbon supported and nitrogen coordinated single Mn site catalysts (Mn-N-C) catalysts are the most desirable platinum group metal (PGM)-free cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their insignificant Fenton reactions (vs. Fe), earth abundances (vs. Co) and encouraging activity and stability. However, current Mn-N-C catalysts suffer from high over-potential due to low intrinsic activity and less dense MnN 4 sites. Herein, we present sulfur-doped Mn-N-C catalyst (Mn-N-C-S) synthesized through an effective adsorption-pyrolysis process. Using electron microscopy and X-ray absorption spectroscopy (XAS) techniques, we verify the uniform dispersion of MnN 4 sites and confirm the effect of S doping on the Mn-N coordination. The Mn-N-C-S catalyst exhibits a favorable oxygen reduction reaction (ORR) activity in acidic media relative to the S-free Mn-N-C catalyst. The corresponding membrane electrode assembly (MEA) generated a remarkable performance with a peak power density of 500 mW cm -2 under a realistic H 2 /air environment. The constant voltage tests of fuel cells confirm the much-enhanced stability of the Mn-N-C-S catalyst compared to the Fe-N-C and Fe-N-C-S catalysts. The electron microscopy and Fourier transform XAS analysis provide insights into catalyst degradation associated with Mn oxidation and agglomeration. The theoretical calculation elucidates that the promoted ORR activity is mainly attributed to the spatial effect stemmed from the repulsive interaction between the ORR intermediates and adjacent S do-pants.

25 ENERGY STORAGE↗

Carbon Corrosion in CO2 Electrolysis Systems

Driven by concerns over climate change, interest in CO2 conversion technologies has dramatically increased in recent years. By viewing CO2 as a readily available feedstock, many pathways for the production of carbon-neutral fuels and chemicals become available. In converting CO2, low carbon emitting energy sources must be used to ensure a low carbon footprint of the fuel and chemical products. The low-temperature electrochemical conversion of CO2 is a promising technology and allows for direct integration with renewable electricity sources. The development of low-temperature CO2 electrolysis technologies is informed by both PEM fuel cells and water electrolyzers, both of which are at a higher stage of development. However, CO2 electrolysis operates at a much higher cell voltage (-3V) than other low-temperature electrochemical processes, which can have implications for materials compatibility in the electrolyzer device. Carbon corrosion is of particular concern for the anode of CO2 electrolyzers, as a large driving force for corrosion exists due to the high required cell potentials. In this presentation, recent observations will be shared on carbon corrosion of the anode gas diffusion electrode (GDE) in low-temperature alkaline exchange membrane CO2 electrolysis. Results from ex-situ tests designed to isolate the carbon corrosion process for anode GDEs will be shared. These results will provide guidance on materials selection for CO2 utilization MEAs, which need to have a lifetime of several years to ensure industrial viability.

BIOMASS FUELS↗

Design of Experiments for Dynamic Test Runs in Solvent-Based CO 2 Capture Pilot Plants

Test runs in the pilot plants consume significant resources, and therefore, the learning from test runs should be maximized. Test runs conducted in the pilot plants are often steady state. It takes several hours for reaching steady-state in the pilot plants, and thus, the duration of the test runs needs to be long even for collecting few steady-state data points. On the other hand, a large number of measurements can be collected through dynamic test runs in a short span of time. This paper presents a systematic design of dynamic experiments (DoDEs) for identifiability of model parameters, which is achieved by persistently exciting the inputs signals. A pseudorandom binary sequence (PRBS) is designed as the input signal for DoDE due to its efficiency in obtaining sufficient spectral content. However, due to the long sequence size of the PRBS signal, a Schroeder-phase input signal, which is a multisine signal, is also designed. Tests for both types of signals are run in the Pilot Solvent Test Unit (PSTU) at the National Carbon Capture Center in Wilsonville, Alabama. The transient data are used to solve dynamic data reconciliation and parameter estimation problem. The estimated parameters are found to be not only superior to those estimated from using data collected from hundreds of steady-state test runs in a nonreactive (air–water) system, but the parameters could be estimated by using the dynamic data collected for about 24 h from the pilot plant for the MEA-H 2 O–CO 2 system.

CO2 capture↗

Regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-Metal Site-Rich Carbon and Pt

Developing low platinum-group-metal (PGM) catalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) for heavy-duty vehicles (HDVs) remains a great challenge due to the highly demanded power density and long-term durability. Here, this work explores the possible synergistic effect between single Mn site-rich carbon (Mn SA -NC) and Pt nanoparticles, aiming to improve intrinsic activity and stability of PGM catalysts. Density functional theory (DFT) calculations predicted a strong coupling effect between Pt and MnN 4 sites in the carbon support, strengthening their interactions to immobilize Pt nanoparticles during the ORR. The adjacent MnN 4 sites weaken oxygen adsorption at Pt to enhance intrinsic activity. Well-dispersed Pt (2.1 nm) and ordered L1 2 -Pt 3 Co nanoparticles (3.3 nm) were retained on the Mn SA -NC support after indispensable high-temperature annealing up to 800 °C, suggesting enhanced thermal stability. Both PGM catalysts were thoroughly studied in membrane electrode assemblies (MEAs), showing compelling performance and durability. The Pt@Mn SA -NC catalyst achieved a mass activity (MA) of 0.63 A mg Pt –1 at 0.9 V iR-free and maintained 78% of its initial performance after a 30,000-cycle accelerated stress test (AST). The L1 2 -Pt 3 Co@Mn SA -NC catalyst accomplished a much higher MA of 0.91 A mg Pt –1 and a current density of 1.63 A cm –2 at 0.7 V under traditional light-duty vehicle (LDV) H 2 –air conditions (150 kPa abs and 0.10 mg Pt cm –2 ). Furthermore, the same catalyst in an HDV MEA (250 kPa abs and 0.20 mg Pt cm –2 ) delivered 1.75 A cm –2 at 0.7 V, only losing 18% performance after 90,000 cycles of the AST, demonstrating great potential to meet the DOE targets.

25 ENERGY STORAGE↗

Lab-scaled performance evaluation of novel water-lean solvents for post combustion CO 2 capture

Here, this work focuses on demonstrating the energetic performance and operational reliability in a continuous system of RTI's water-lean solvents for post-combustion CO 2 capture applications. RTI's Non-Aqueous Solvent, NAS-1A was subjected to 100 h of continuous, CO 2 capture and regeneration operation using a Lab-scale Gas Absorption System (LsGAS) while the CO 2 capture efficiency, mass balance, and total energy inputs were monitored. Throughout the test period, NAS-1A demonstrated stable operation with 90% CO 2 capture while requiring about 15% lower total energy input for solvent regeneration compared to 30 wt% monoethanolamine (MEA) solution. The use of a slipstream of CO 2 -rich solvent from the absorber sump reduced the regenerated CO 2 temperature before the gas was further cooled by the overhead condenser at the top of the desorber. The rich-split setup combined with a wash section may be an effective approach to remove water and solvent vapor from the regenerated CO 2 as well as to recover heat at the top of the desorber. NAS-1B was later developed and included a modifier component that lowers the heat of CO 2 absorption and reduces the vapor pressure of the amine component. The total energy inputs for 90% CO 2 capture with NAS-1B was found to be 25% less than that of the MEA. A gas chromatograph was used to monitor the amine concentration in the gas leaving the absorber wash section. It was found that under similar operating conditions, the presence of the modifier in NAS-1B reduces the amine in the absorber off-gas from 143 ppm in NAS-1A to 20 ppm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Current Density Durability of Pt/C and PtCo/C Catalysts at Similar Particle Sizes in PEMFCs

The durability of carbon supported PtCo-alloy based nanoparticle catalysts play a key role in the longevity of proton-exchange membrane fuel cells (PEMFC) in electric vehicle applications. To improve its durability, it is important to understand and mitigate the various factors that cause PtCo-based cathode catalyst layers (CCL) to lose performance over time. These factors include i) electrochemical surface area (ECSA) loss, ii) specific activity loss, iii) H + /O 2 -transport changes and iv) Co 2+ contamination effects. We use a catalyst-specific accelerated stress test (AST) voltage cycling protocol to compare the durability of Pt and PtCo catalysts at similar average nanoparticle size and distribution. Our studies indicate that while Pt and PtCo nanoparticle catalysts suffer from similar magnitudes of electrochemical surface area (ECSA) losses, PtCo catalyst shows a significantly larger cell voltage loss at high current densities upon durability testing. The distinctive factor causing the large cell voltage loss of PtCo catalyst appears to be the secondary effects of the leached Co 2+ cations that contaminate the electrode ionomer. A 1D performance model has been used to quantify the cell voltage losses arising from various factors causing degradation of the membrane electrode assembly (MEA).

08 HYDROGEN↗

Ferroelectricity of wurtzite Al 1−x Hf x N heterovalent alloys

Thin films of aluminum hafnium nitride (Al1−xHfxN) were synthesized via reactive magnetron sputtering for Hf contents up to x = 0.13. X-ray diffraction showed a single c-axis oriented wurtzite phase for all films. Hard x-ray photoelectron spectroscopy demonstrated homogeneous Al:Hf distribution through the thin films and confirmed their insulating character. A collection of complementary tests showed unambiguous polarization inversion, and thus ferroelectricity in multiple samples. Current density vs electric field hysteresis measurements showed distinct ferroelectric switching current peaks, the piezoelectric coefficient d 33,f,meas measured using a double beam laser interferometer (DBLI) showed a reversal in sign with similar magnitude, and anisotropic wet etching confirmed field-induced polarization inversion. This demonstrates the possibility of using tetravalent–and not just trivalent–alloying elements to enable ferroelectricity in AlN-based thin films, highlighting the compositional flexibility of ferroelectricity in wurtzites and greatly expanding the chemistries that can be considered for future devices.

36 MATERIALS SCIENCE↗