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Interfacial design using strategically chosen linkers, like cysteamine, can effectively mitigate confinement effects in ionomer thin films and improve proton transport in targeted directions.
Laser-driven ion beams have gained considerable attention for their potential use in multidisciplinary research and technology. Preclinical studies into their radiobiological effectiveness have established the prospect of using laser-driven ion beams for radiotherapy. In particular, research into the beneficial effects of ultrahigh instantaneous dose rates is enabled by the high ion bunch charge and uniquely short bunch lengths present for laser-driven ion beams. Such studies require reliable, online dosimetry methods to monitor the bunch charge for every laser shot to ensure that the prescribed dose is accurately applied to the biological sample. In this paper, we present the first successful use of an Integrating Current Transformer (ICT) for laser-driven ion accelerators. This is a noninvasive diagnostic to measure the charge of the accelerated ion bunch. It enables online estimates of the applied dose in radiobiological experiments and facilitates ion beam tuning, in particular, optimization of the laser ion source, and alignment of the proton transport beamline. We present the ICT implementation and the correlation with other diagnostics, such as radiochromic films, a Thomson parabola spectrometer, and a scintillator.
The practical description of disordered chemical reactions, where the reactions involve multiple species at multiple sites, is presently a challenge using correlated electronic structure methods due to their high computational cost and steep scaling. Here, we describe the gradient theory of multi-fragment density matrix embedding theory, which potentially provides a minimal computational framework to model such processes at the correlated electron level. We present the derivation and implementation of the gradient theory, its validation on model systems and chemical reactions using density matrix embedding, and its application to a molecular dynamics simulation of proton transport in a small water cluster, a simple example of multi-site reaction dynamics.
Recent development of reactive force fields have enabled molecular dynamics simulations of interactions between silicate glasses and water at the atomistic scale. While multicomponent silicate glasses encompass a wide variety of compositions and properties, one common structural feature in these glasses is the combination of the network structure that is made up of silica tetrahedra linked through corner sharing interspersed with network modifiers like alkali and alkaline-earth ions that break up the Si–O–Si linkages by forming nonbridging oxygen. In reactions with water, ion exchange between alkali ions in the glass and proton or hydronium in the solution, as well as hydrolysis reaction of the Si–O–Si linkages and subsequent silanol formation, is observed and well documented. Furthermore, we have used a set of recently developed reactive force field to investigate the reactions between water and the surfaces of silica and sodium silicate glasses of different compositions for reactions up to 8 nanoseconds. Our results indicate sodium leaching into water and diffusion of water molecules up to 25 Å into the glass surface. We examined the structural and compositional changes inside the glass and around the diffused ions and use these to explain the rates of silanol formation at the surface. We also observed proton transport in the glass which has an indirect influence on the silanol formation rates. While the surface of the glass was rough to start with, it undergoes further modification into a hydrated gel-like structure in the glass for up to 5 Å in the higher alkali containing glasses. It was found that the leached sodium ions remain close to the interface and that fragments of silicate network from the surface is capable of dislodging from the bulk glass and enter the aqueous solution. These simulations thus provide insights into the formation and structure of an alteration layers commonly observed in multicomponent silicate glasses corroded in aqueous solutions.
Abstract Grain boundaries in protonic ceramic cell (PCC) electrolytes hinder proton transport, reducing interfacial conductivity. In multicomponent PCC electrolytes, the inclusion of sintering aids further accentuates the complexity of grain boundaries. In this study, we synthesize nanocrystalline BaCe 0.4 Zr 0.4 Y 0.1 Yb 0.1 O 3− δ thin films via pulsed laser deposition and analyze their grain boundary character distributions using orientation data collected by precession electron diffraction technique. The results reveal an anisotropic distribution of grain boundary characters, with notably high populations of 180°‐tilt and twist grain boundaries. These findings provide critical insights into identifying the predominant grain boundaries in this PCC electrolyte material, assessing the vast five‐dimensional grain boundary space.
The all-iron flow battery is currently being developed for grid scale energy storage. As with all flow batteries, the membrane in these systems must meet stringent demands for ionic conductivity while limiting unwanted reactant (Fe 3+ ) crossover. In addition, for the all-iron chemistry proton transport across the membrane is highly desirable to maintain the pH levels in the negative and positive electrolytes. Two membranes are considered, Nafion and an in-house developed composite based on Daramic (a commercial microporous separator) and poly(vinyl alcohol). Their performance is compared for various metrics specific to the all-iron flow battery chemistry.
The Oak Ridge National Laboratory (ORNL) is implementing a major upgrade to the Spallation Neutron Source (SNS) facility, encompassing the addition of the Second Target Station (STS). Preliminary design reviews have been conducted on several STS Personnel Protection Systems (PPS). The reviews focused primarily on the integration with the existing SNS PPS, the new proton transport tunnel, and the target areas. Development of the PPS is ongoing, to ensure a coherent safety system with the mission of protecting users and workers from prompt radiation hazards while providing high beam availability to operations. The STS PPS element in the Integrated Control System (ICS) is a facility-wide system composed of multiple safety subsystems, including the Ring to Second Target (RTST) beam transport tunnel, Target, Bunker and Instruments. Personnel working in all these geographic areas are protected by modular reliable PPS solutions. The safety system enforces access controls, radiation monitoring, beam destination control, and application of critical device inhibit upon detection of abnormal condition. It uses well-documented processes, Common Industrial Protocol (CIP) safety, pulsed test, and redundancy to achieve the desired Safety Integrity Level (SIL). This paper gives an architectural overview of the STS PPS and a detailed safety plan for the SNS facility, addressing safety solutions and human factors.
The goal of this project was to fabricate and study the performance and durability implications of thin, mechanically reinforced membranes containing gas recombination catalysts (GRCs) for advanced proton exchange membrane water electrolysis (PEMWE) systems. The thinner membranes, optimized for a PEMWE environment, dramatically reduced the proton transport resistance across the membrane, improving the overall efficiency of the PEMWE system. At the same time, the GRC technology was deployed to recombine crossover hydrogen from the cathode with oxygen from the anode to form water within the membrane. This reaction mitigated the buildup of hydrogen in the oxygen stream, ensuring safe operation of the PEMWE system. Capabilities to measure the gas crossover in both an ex-situ screening cell and in operando application testing were developed over the course of the project to track membrane progress and quantify deliverables. State of the art roll to roll manufacturing technologies were leveraged to fabricate the membranes on a commercial scale, where the membrane structure was precisely tuned and GRC distributed within the membrane structure.
Proton exchange membrane water electrolysis (PEMWE) is a promising option for hydrogen production from a variety of energy sources. Cost-effective production of hydrogen with PEMWE requires reduction of costly precious metals as well as optimization of the components and interfaces in the cell. The interface between the platinum-coated titanium porous transport layer (PTL) and catalyst layer (CL) significantly impacts the performance of the electrolyzer cell. Here, we report on two PTL modification methods, mechanical abrasion and chemical etching, which we find improve PEMWE performance by lowering the resistance of the PTL/CL interface. The PTL surface modifications enabled performance improvements up to 77 mV at 4 A cm −2 and reduction of the high frequency resistance, demonstrating that the resistance of the PTL/CL interface is a significant factor in the cell performance. The PTL surface roughness was varied using abrasive materials ranging from 0.1 to 140 μm in grain sizes and chemical etching was found to also increase the surface roughness. The surface roughness was quantified using confocal laser microscopy and the surface oxidation was measured using X-ray photoemission spectroscopy. These results demonstrate that both increasing surface roughness and oxide removal contribute to lowering the PTL/CL interfacial resistance and increasing cell performance.
Density functional theory-based thermodynamic modeling was performed to determine the effect of humidity and H 2 /O 2 gas pressure on the defect chemistry and transport properties of proton conducting oxide BaZr 1-x Y x O 3-δ (x ≤ 0.1) in the temperature range of 800–1200K, relevant for solid oxide fuel/electrolysis cell applications. The first-principles charge defect analysis was carried out to obtain the defect energetic ensembles as a function of Fermi level as well as the dependence of the hydration and oxidation reaction energies on complex defect-dopant configurations. It is shown that oxygen vacancies introduced to compensate for the extra Ba vacancies may cause a slight increase in the concentration of hydroxyl and proton species upon hydration of Ba deficient BaZr 1-x Y x O 3-δ , while the overall proton diffusivity is predicted to decrease with increased proton hopping barriers upon trapping near the Ba vacancies. The developed defect model is further demonstrated to be able to describe the bulk defect chemistry and transport properties of BaZr 0.9 Y 0.1 O 3-δ under the solid oxide cell operating conditions. Finally, the theoretical framework developed in this work further allows the inclusion of configurational, energetic and electronic characteristics of the defects that can be used as a complementary tool to experimental measurements for testing various mechanistic pathways or to provide essential mechanistic data.
Laser-accelerated proton beams are applicable to several research areas within high-energy density science, including warm dense matter generation, proton radiography, and inertial confinement fusion, which all involve transport of the beam through matter. Here, we report on experimental measurements of intense proton beam transport through plastic foam blocks. The intense proton beam was accelerated by the 10 ps, 700 $\textit{J}$ OMEGA EP laser irradiating a curved foil target, and focused by an attached hollow cone. The protons then entered the foam block of density 0.38 g/cm 3 and thickness 0.55 or 1.00 mm. At the rear of the foam block, a Cu layer revealed the cross section of the intense beam via proton- and hot electron-induced Cu-K α emission. Images of x-ray emission show a bright spot on the rear Cu film indicative of a forward-directed beam without major breakup. 2D fluid-PIC simulations of the transport were conducted using a unique multi-injection source model incorporating energy-dependent beam divergence. Along with postprocessed calculations of the Cu – $K_α$ emission profile, simulations showed that protons retain their ballistic transport through the foam and are able to heat the foam up to several keV in temperature. The total experimental emission profile for the 1.0 mm foam agrees qualitatively with the simulated profile, suggesting that the protons indeed retain their beamlike qualities.
Both electron-rich and electron-poor perovskite oxides have been used in solid oxide cell applications as electrode and electrolyte materials. The rich oxygen defect chemistry and its coupling to temperature, hydrogen-steam or oxygen-steam gas pressure, or to the applied potentials creates enormous complexities for modeling performance and degradation of the materials. Herein, density functional theory-based thermodynamic modeling was carried out to describe the defect chemistry and transport properties of the proton-conducting electrolyte BaZr1-xYxO3-δ (x≤0.1) and of the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr). The defect thermodynamics of intrinsic point defects and the hydrogen-related defect reactions were solved in integrated defect models and further used to predict the Brouwer diagram and the transport properties of the functional perovskites. For the electron-poor electrolytes BaZr0.9Y0.1O3-δ, the developed model has been used to describe the experimental transport properties in the SOC operating conditions. Specifically, the roles played by the acceptor-bound holes and the intrinsic and hydrogen point defects upon the conductivities of holes, protons, and oxygen vacancies under the hydrogen-rich and oxygen-rich conditions at various humidity levels were demonstrated. A defect modeling tool was also developed for the triple-conducting perovskite (La,Ba)(Fe,M)O3-δ (M=Y and Zr) to examine magnetic effects and hydride defects in defect equilibria.
The human peptide transporter hPEPT1 (SLC15A1) is responsible for uptake of dietary di- and tripeptides and a number of drugs from the small intestine by utilizing the proton electrochemical gradient, and hence an important target for peptide-like drug design and drug delivery. hPEPT1 belongs to the ubiquitous major facilitator superfamily that all contain a 12TM core structure, with global conformational changes occurring during the transport cycle. Several bacterial homologues of these transporters have been characterized, providing valuable insight into the transport mechanism of this family. Here we report the overexpression and purification of recombinant hPEPT1 in a detergent-solubilized state. Thermostability profiling of hPEPT1 at different pH values revealed that hPEPT1 is more stable at pH 6 as compared to pH 7 and 8. Micro-scale thermophoresis (MST) confirmed that the purified hPEPT1 was able to bind di- and tripeptides respectively. To assess the in-solution oligomeric state of hPEPT1, negative stain electron microscopy was performed, demonstrating a predominantly monomeric state.
Thin foil based porous transport layers (PTLs) that contain highly structured pore arrays have shown promise as anode PTLs in proton exchange membrane electrolysis cells. These novel PTLs, fabricated with advanced manufacturing techniques, produce thin, tunable, multifunctional layers with reduced flow and interfacial resistances and high thermal and electric conductivities. To further optimize their design, it is important to understand their fundamental impact on the transport of protons, electrons, and liquid/vapor mixtures in the electrode. In this work, we develop a two-dimensional multiphysics model to simulate the coupled electrochemistry and multiphase transport in an electrolysis cell operated with the novel PTL architecture. The results show that larger pores improve access of water to the anode catalyst layer, which is beneficial for both the oxygen evolution reaction and membrane hydration. Larger pore sizes also improve oxygen gas transport from the catalyst layer, because generated oxygen gas is forced to travel in-plane through the anode catalyst layer until it reaches a pore opening that is connected to a channel. The discussed results confirm that the proposed thin foil based PTLs are fundamentally different from conventional PTLs, such as felts or layered meshes. The model developed in this work also provides generalizable insight into fundamental PEMEC phenomena, such as the competition between liquid and gas phase transport, membrane hydration and water management, and nonuniform electrochemical reactions, which are processes relevant to all PEMEC designs.
Concentrated hydrogen-bonded electrolytes (CoHBEs) are structured, electrochemically stable, less-volatile alternatives to aqueous and dilute nonaqueous electrolytes, however, with high viscosities that limit molecular diffusion. This work provides an understanding of the proton conduction mechanism in CoHBEs based on mixtures of acids and azoles and establishes a link between the structurally dictated transport properties and the proton-coupled electron transfer (PCET) reaction rates that can be leveraged for enhancing electrochemical reactions. Diffusion and relaxation NMR studies suggest a breaking of the viscosity–conductivity tradeoff, where at high azole concentrations (>45 mol%), Grotthuss transport is more likely with lowered proton transfer energy barriers between the azole and the acid according to the machine learning (ML) accelerated ab initio path integral MD (AI-PIMD) simulations. Proton conduction pathways are found to be switchable between the hydrogen bonding networks of the acid and the azole, with imidazole chain forming structures better facilitating Grotthuss hopping. Supported by small-angle neutron scattering studies, the chains are found to have six member molecules on average with maximum of 3 to 4 imidazole/imidazoliums at 50 to 60 mol%. Despite their high viscosities, the measured PCET rates for quinones and phenazines measured in the protic CoHBEs present relatively high electron transfer rate constants (k 0 ~ 10 −4 cm/s), validated by rotating disc electrode and scanning electrochemical microscopy measurements. The results demonstrate that strategic tuning of hydrogen-bond donor–acceptor interactions enables the decoupling of proton transport and viscosity, thereby impacting PCET reactions.
47th International Conference and Expo on Advanced Ceramics and Composites (ICACC 2023), Daytona Beach, FL, January 22-27, 2023
23rd Annual Solid Oxide Fuel Cell (SOFC) Project Review Meeting, Pittsburgh, PA, October 25-27, 2022
The ionomer content in platinum group metal (PGM)-free polymer electrolyte fuel cell (PEFC) cathode catalyst layer (CCL) plays an important role in the electrode gas transport properties, proton conductivity, and hence, membrane electrode assembly (MEA) performance. In this work, the ionomer content in the CCL is varied, influencing electrode microstructure by altering porosity, tortuosity, as well as ionomer distribution and coverage of the catalyst particles. A novel technique consisting of a H 2 pump, combined with a Pt black sensor layer, is used to measure the bulk mass transport resistance of a series of PGM-free CCL prepared with different ionomer contents. The values for bulk electrode mass transport resistance are contrasted with electrode proton transport resistance in the cathode catalyst layer, establishing a clearly defined trade-off between two key performance limiting phenomena and identifying a need for novel PGM-free electrode fabrication strategies.