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At least 145 records · Page 8

Studies of Localization Effects on Transverse Kinematic Imbalance in the GENIE Generator

The forthcoming Deep Underground Neutrino Experiment (DUNE) requires precise modeling of neutrino--nucleus interactions to achieve its neutrino-oscillation measurement goals. GENIE, the Monte Carlo event generator used by DUNE and other Fermilab-based experiments as a central value model for neutrino-nucleus cross sections, exhibits known discrepancies in comparison to MicroBooNE cross section data, especially when considering neutrino scattering events' transverse kinematic imbalance (TKI). For quasielastic-like measurements, the data show a larger transverse missing momentum tail while maintaining a peak similar to that predicted by the baseline GENIE model. Previous attempts at a solution include variations of final-state interaction (FSI) strengths, incorrectly decreasing both the peak and tail, thus leaving the discrepancy unresolved. This work investigates whether inconsistencies between local and global treatments of intranuclear physics contribute to the observed mismodeling. In this work, GENIE FSI routines have been modified to directly utilize intranuclear particle positions, thereby introducing a newly localized momentum treatment in correlation with the nominal density in both the hA and hN intranuclear cascade models for their 2018 and 2025 variants. Meson-exchange-current (MEC) localization was also tested for the hN 2018 model. Comparisons of the intranuclear nucleons' ("scattering center") momentum and its radial dependence validate the localization implementation. However, while such consistent localization produces modest changes in the proton momentum spectrum at low-to-medium momenta, only small changes are observed in the TKI distributions. These changes are insufficient to account for the discrepancy with MicroBooNE data. Although a localized treatment improves the internal consistency of the GENIE model, the origin of the TKI discrepancy remains unresolved by such a solution.

Bulla, Braden [Ctr. Coll., Danville; Fermilab]↗

Understanding Recoverable vs Unrecoverable Voltage Losses and Long-Term Degradation Mechanisms in Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently shown excellent progress in terms of their performance – e.g., achievable power and current density. However, very few AEMFCs have been demonstrated with the ability to operate for a long duration (>1000 h). In addition, it is unknown whether performance losses observed during operation are reversible, irreversible, or a combination of the two. In this study, a high-performance AEMFC operated continuously at 600 mA/cm 2 for 3600 h (150 days) at 80 °C with H 2 /O 2 reacting gases was demonstrated. Throughout testing, the electrochemical properties of the AEMFC were probed to provide information about performance degradation pathways and their degree of reversibility. It was found that a portion of the performance loss that occurs during AEMFC operation was due to suboptimal reaction conditions and can be recovered. At the end of the experiment, the cell was disassembled, and its structure and composition were evaluated at the nanoscale by aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. The structure and composition of the electrode were compared to cells at the beginning of their operational life. It was found that the primary mechanism for long-term AEMFC performance loss was catalyst agglomeration. During the operational time, there was no evidence of significant polymer degradation, likely due to the high hydration state of the cell. By documenting the long-term changes in high-performing AEMFCs, this work provides important information for the systematic design of cell components and demonstrates the importance of controlling cell operation, which can aid in the commercialization and widespread deployment of low-cost, long-life AEMFCs.

30 DIRECT ENERGY CONVERSION↗

Development of a High Reliability Compact Air Independent PEMFC Power System

Autonomous Underwater Vehicles (AUV's) have received increasing attention in recent years as military and commercial users look for means to maintain a mobile and persistent presence in the undersea world. Compact, neutrally buoyant power systems are needed for both small and large vehicles. Historically, batteries have been employed in these applications, but the energy density and therefore mission duration are limited with current battery technologies. Vehicles with stored energy requirements greater than approximately 10 kWh have an alternate means to get long duration power. High efficiency Proton Exchange Membrane (PEM) fuel cell systems utilizing pure hydrogen and oxygen reactants show the potential for an order of magnitude energy density improvement over batteries as long as the subsystems are compact. One key aspect to achieving a compact and energy dense system is the design of the fuel cell balance of plant (BOP). Recent fuel cell work, initially focused on NASA applications requiring high reliability, has developed systems that can meet target power and energy densities. Passive flow through systems using ejector driven reactant (EDR) circulation have been developed to provide high reactant flow and water management within the stack, with minimal parasitic losses compared to blowers. The ejectors and recirculation loops, along with valves and other BOP instrumentation, have been incorporated within the stack end plate. In addition, components for water management and reactant conditioning have been incorporated within the stack to further minimize the BOP. These BOP systems are thermally and functionally integrated into the stack hardware and fit into the small volumes required for AUV and future NASA applications to maximize the volume available for reactants. These integrated systems provide a compact solution for the fuel cell BOP and maximize the efficiency and reliability of the system. Designs have been developed for multiple applications ranging from less than 1 kWe to 70 kWe. These systems occupy a very small portion of the overall energy system, allowing most of the system volume to be used for reactants. The fuel cell systems have been optimized to use reactants efficiently with high stack efficiency and low parasitic losses. The resulting compact, highly efficient fuel cell system provides exceptional reactant utilization and energy density. Key design variables and supporting test data are presented. Future development activities are described.

Vasquez, Arturo↗

The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO

The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fast and Simple Ag/Cu Ion Exchange on Cu Foil for Anode-Free Lithium-Metal Batteries

Lithium-metal batteries with zero excess lithium on the anode side paired with a fully lithiated cathode are regarded as a form of the highest energy-density configuration. Unfortunately, the continuous lithium loss over cycling from a limited amount of lithium reservoir significantly degrades the overall cell performance in the anode-free system. To mitigate the deterioration, modifying the current collector for enhanced lithium cycling is an indispensable route. Here, we apply a Ag/Cu ion exchange to precipitate micro-sized Ag particles on the Cu current collector to enhance the lithium reversibility via (de)alloying process. Further, we show a smoother morphology of lithium upon alloying, which leads to a lowered nucleation potential as well as increased average Coulombic efficiency in Li||Cu cells regardless of electrolyte formulation. The preferred lithium adsorption on Ag and AgLi over Cu is demonstrated with density functional theory calculations, which supports that Li is forming a gamma-phase alloy in the last stage rather than being deposited beneath the alloy. Lastly, this simple Cu foil modification enhances lithium reversibility and reduces its nucleation barrier, thus mitigating the capacity fade of a Cu||LiFePO 4 with reduced polarization.

25 ENERGY STORAGE↗

Linking structure to performance: Characterization of porous transport layers for high-pressure water electrolysis

Proton exchange membrane (PEM) water electrolysis is a promising technology to produce cost-efficient hydrogen. PEM electrolyzers offer a large current density range and the ability to operate at differential pressure which can be used to minimize both capital and operational expenditures. However, directly producing pressurized hydrogen at the cathode results in pushing the membrane against the anode porous transport layer (PTL). This can lead to detrimental effects, such as membrane deformation or ruptures, which depend on membrane properties as well as PTL material properties such as pore size, structure, and morphology. In this work, a range of sinter and felt-based commercial PTLs are evaluated for their contributions to the cell's electrochemical and H 2 crossover performance at cathode pressures up to 30 bar. X-ray tomography and post-operando optical microscopy are used to assess the morphology of the PTLs, and the PTL induced deformation experienced by the catalyst coated membrane (CCM), respectively. PTL samples with lower porosity were found to reduce both the cell voltage and the amount of H 2 permeating from the cathode to the anode exhaust, which was ascribed to improved catalyst layer contact and reduced membrane deformation, respectively. The best performing PTLs improved electrolyzer efficiency by ~1.5 kWh/kg H2 . Specifically, 1 kWh/kg H2 was gained due to reducing membrane deformation and decreasing H 2 crossover. The remainder 0.5 kWh/kg H2 were achieved by improving the electrical contact at the electrode/PTL interface which decreased cell voltage.

08 HYDROGEN↗

Bipolar Membranes for Ion Management in (Photo)Electrochemical Energy Conversion

Conspectus (Photo)electrochemical energy conversion is important in the development of a carbon-neutral energy economy because it can provide a pathway for mitigating the intermittency of renewable energy sources such as wind and solar. In order to operate efficiently, these technologies, which include photoelectrochemical cells, water and CO 2 electrolyzers, fuel cells, and redox flow batteries, require fast charge transfer kinetics at the electrode/electrolyte interface as well as robust ion management in the electrolyte. In conventional electrolyzers and fuel cells, the electrolyte is strongly acidic or basic and ionic current is carried by H + or OH – ions. In contrast, photoelectrodes and electrocatalysts for water splitting are often studied in buffered solutions. The question of ion balance in these systems led us to analyze the polarization losses due to ion concentration gradients in cells that employed various buffer–membrane combinations. Continuously driving the buffer ions across an ionomer membrane not only lowers the buffer capacity of an aqueous electrolyte but also introduces pH gradients that result in significant energy losses. To address the problem, we and other groups have studied the use of reverse-biased bipolar membranes (BPMs) in (photo)electrolytic cells. BPMs consist of an anion exchange layer (AEL) laminated with a cation exchange layer (CEL) and are usually equipped with a catalytic layer in between to accelerate the water dissociation reaction. At the AEL/CEL interface, water dissociates into protons and hydroxide ions, which replenish those consumed at the cathode and anode. Compared to conventional water electrolyzers with proton/anion exchange membranes (PEM/AEM), BPM electrolyzers provide the unique advantage of continuously operating the cathode and anode under different pH conditions, which is desirable when the two electrode reactions have different pH requirements. BPMs also enable the use of buffered electrolytes at pH values that are optimized for electrode stability and product selectivity in applications such as CO 2 electrolysis. Product crossover losses and CO 2 pumping can be dramatically reduced in BPM-based CO 2 electrolyzers, relative to conventional alkaline membranes, by electrostatic repulsion (of anionic products) and electroosmotic drag (for neutral products). BPM-based gas fed CO 2 electrolyzers can achieve high current density, but they suffer from low Faradaic efficiency (FE) due to the acidic local environment of the CEL. This problem can be mitigated by adding an aqueous buffering layer or by creating a weak acid cation exchange film on the CEL face of the membrane. The use of BPMs in fuel cells and redox flow batteries offers some interesting advantages. Configurations with both reverse and forward bias have been studied, but forward bias has been favored due to material compatibility, reaction kinetics, and thermodynamic considerations. The net reaction at the AEL/CEL interface is the acid–base neutralization reaction, which has a high inherent reaction rate constant, but in the BPM is limited to a nanometric space-charge layer and requires efficient catalysis to achieve high current density. Understanding the mechanism of the acid–base neutralization and the opposite process, the water dissociation reaction, will be essential for improving the performance of forward-biased BPMs. In conclusion, this Account reviews our current understanding of the working mechanisms of BPMs and discusses how we can use them to effectively manage ions for various (photo)electrochemical applications.

Yan, Zhifei↗

System Integration of Rationally Designed Dilute Alloy Catalysts for Energy-Efficient Electrochemical CO 2 -To-Fuel Conversion

Energy effiecient electrochemical conversion of CO 2 to high-demand chemicals and transportation fuels using renewable solar and wind energy is a key technology needed for a high-productivity, low-carbon future. However, the development of scalable, low-cost, active, selective, and stable electrocatalysts remains a key challenge that needs to be overcome to enable high-volume conversion of CO 2 to feedstock chemicals for the chemical industry. In previous work, Lawrence Livermore National Laboratory (LLNL) has developed a rational design platform for dilute alloy transition metal electrocatalysts that promise to make electrochemical CO 2 conversion more energy efficient and selective. In this project, we worked with our industrial partners, Twelve and TotalEnergies, to improve scale up, integration, and stability of LLNL’s dilute alloy catalyst technology into an industry-relevant zero gap electrolyzer platform. Through virtual experiments and data analysis, we designed efficient and cost-effective copper-based catalysts. The catalyst was specifically designed to streamline the slowest and most energy-intensive step of the electrochemical chemical transformation of CO 2 to multi-carbon products – that is making the carbon-carbon bond by dimerization of the reaction intermediate carbon monoxide - resulting in up to 10% improvement in energy efficiency for C 2 products while simultaneously increasing the selectivity towards C 2 products. We tested two different scalable catalyst coating technologies and down-selected magnetron sputtering as the technique that provided the best control over catalyst loading, composition, and morphology. Using this technology, we successfully demonstrated integration of our dilute alloy catalysts into a 100 cm 2 electrolyzer platform with Faradaic efficiencies for ethylene production reaching 40% at a current density of 200 mA/cm 2 . We also developed the technology to integrate a well-defined nanoscale porosity by depositing alloy compositions that were compatible with dealloying, that is, selective leaching of an alloy component to generate nanoscale porosity. We observed that integration of the dealloying-derived nanoporosity improved catalyst performance and stability by leading to a more hydrophobic catalyst/anion exchange membrane interface. Unsolved problems that still need to be addressed are corrosion of the Cu catalyst -specifically if the used catalyst is exposed to air - as well as long term stability do to salt formation/deposition and flooding of the catalyst/electrolyzer flow channels, especially at higher current densities. As we only worked on optimization of catalyst composition, coating thickness, and morphology, further performance optimization will require a system level approach that includes optimization of electrolyzer design and membrane technology.

36 MATERIALS SCIENCE↗

Propagation of charge-exchange plasma produced by an ion thruster

A charge-exchange plasma is produced downstream of ion thrusters by collisions between energetic ions and neutrals escaping through the ion optics. The charge-exchange ions flow radially from the thruster beam due to electric fields produced by its density gradient. The propagation of the charge-exchange plasma after it leaves the thruster beam is the subject of this paper. Under the proper conditions there is an 'end-effect' of a long, cylindrical Langmuir probe which allows a significant increase in collected ion current when the probe is aligned with a flowing plasma. This effect is used to determine the charge-exchange plasma flow direction at various locations relative to the ion thruster. A portion of the charge-exchange plasma flows upstream of the ion thruster and can represent a contamination source to electrically propelled spacecraft. The ion current collected by the probe as a function of its angle with respect to the plasma flow allows determination of the plasma density and plasma flow velocity at the probe's location upstream of the ion thruster optics. The density value obtained from the ion current agree to within a factor of two of density values obtained by typical voltage-current Langmuir probe characteristics.

Carruth, M. R., Jr.↗

The Earth's Exosphere and Its Response to Space Weather

Neutral-Plasma charge exchange is a fundamental physical process that occurs ubiquitously across the universe. In geospace, charge exchange occurs in the Earth’s topside ionosphere, polar wind, plasmasphere, inner magnetosphere, and magnetosheath. Past and current space missions have profiled plasma and electromagnetic characteristics in various parts of the Earth’s magnetospheric system. However, observations of the exosphere, i.e., neutrals above 500 km altitude, are still sparse and, in some regions, non-existent, which limits our understanding of the neutral contribution to the overall dynamics of the geospace environment. Cold exospheric neutrals (< 10 eV) play an important role in the Sun-Earth interaction. Variability of exospheric density provides key information of the Earth’s atmospheric loss under dynamic space environment conditions. Various neutral species and their density variations in the polar wind can alter ion outflow patterns, modifying global magnetospheric dynamics. Exospheric neutrals also provide an energy sink for the inner magnetosphere by creating Energetic Neutral Atoms (ENAs) through charge exchange with high-energy ring current ions, which subsequently leave our geospace system unimpeded by magnetic fields. Exospheric neutrals also provide a means to observe the global interaction of the solar wind – magnetosphere, through global imaging of the system via ENAs (e.g., the TWINS and IMAGE missions) and soft X-rays (e.g., the upcoming LEXI and SMILE missions), the byproducts of neutral-plasma charge exchange. In the coming decade, we advocate that our community needs to increase our exploration of the neutral populations in the outermost reaches of the Earth’s atmosphere. It is imperative that we improve both in-situ and remote-sensing technologies for measuring key neutral species in our exosphere. We also encourage dedicated exosphere missions and to stimulate model developments of our exosphere and its interaction with the co-located magnetospheric system and neighboring Ionosphere - Thermosphere - Mesosphere system.

Hyunju Connor↗

Tri‐Metallic Catalyst for Oxygen Evolution Reaction Enables Continuous Operation of Anion Exchange Membrane Electrolyzer at 1A cm −2 for Hundreds of Hours

Abstract Although numerous efforts are made to synthesize active electrocatalysts for green hydrogen production; catalyst stability, and facile synthesis to scale up the production are still challenging. Herein, the production of novel non‐PGM catalysts for the oxygen reduction reaction (OER) in an alkaline aqueous medium is reported, which is based on the synthesis of a trimetallic metal–organic framework (MOF) precursors. Fine‐tuning of the composition of the metal centers (Ni, Co, and Fe) shows a great effect on OER activity after the MOF undergoes dynamic chemical and structural transformations under OER conditions. In situ characterization reveals the origin of OER activity enhancement as metals’ oxidation state increases, inducing compressive mechanical strain on metal centers, enhancing the electronic conductivity through the formation of oxygen vacancies, and stronger metal–oxygen covalency. Catalysts are used in membrane electrode assembly (MEA) setup within an industrial full‐cell anion exchange membrane electrolyzer (AEMEC), showing a stable performance for 550 h without noticeable decay at 750 and 1000 mA cm −2 industrial level current densities.

Chemistry↗

Nonempirical Range-Separated Hybrid Functional with Spatially Dependent Screened Exchange

Electronic structure calculations based on density functional theory (DFT) have successfully predicted numerous ground-state properties of a variety of molecules and materials. However, exchange and correlation functionals currently used in the literature, including semilocal and hybrid functionals, are often inaccurate to describe the electronic properties of heterogeneous solids, especially systems composed of building blocks with large dielectric mismatch. Here, in this study, we present a dielectric-dependent range-separated hybrid functional, screened-exchange range-separated hybrid (SE-RSH), for the investigation of heterogeneous materials. We define a spatially dependent fraction of exact exchange inspired by the static Coulomb-hole and screened-exchange (COHSEX) approximation used in many-body perturbation theory, and we show that the proposed functional accurately predicts the electronic structure of several nonmetallic interfaces, three- and two-dimensional, pristine, and defective solids and nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced electric propulsion research - 1990

An experimental study of impingement current collection on the accelerator grid of an ion thruster is presented. The equipment, instruments, and procedures being used to conduct the study are discussed. The contribution to this current due to charge-exchange ions produced close to the grid is determined using a volume-integration procedure and measured ion beam current design, computed neutral atom density and measured beam plasma potential data. This current, which is expected to be almost equal to that measured directly, is found to be an order of magnitude less. The impingement current determined by integrating the current density of ambient ions in the beam plasma close to the grid is found to agree with the directly measured impingement current. Possible reasons for the disagreement between the directly measured and volume integrated impingement currents are discussed.

Monheiser, Jeffery M.↗

New model for the ion collection by cylindrical probes over a wide range of collisionality

Langmuir probes remain one of the most important diagnostic tools for plasma processing applications. Modern probe analysis usually relies on the electron current part of the Langmuir probe characteristic using the Druyvesteyn method. However, for electronegative plasmas or for discharges containing dust the analysis of the ion current attracted by the probe can be desirable to determine the ion density. But, even at low pressures of a few Pa, the ion current is affected by collisions due to the large cross section for charge exchange. Available theories for collisional or collision-enhanced ion currents onto probes are complex and not well validated. Thus, in this contribution, we compare available collisional probe theories for the ion current to results of particle-in-cell (PIC) simulations. To this end, the probe surrounded by a semi-infinite plasma is simulated using a modified version of the open-source code EDIPIC. A dataset of currents for different neutral gas pressures is obtained and compared to the different theories from the literature. Based on these results, we propose a simpler and more intuitive model for the ion current collected by the probe, based on the model of Gatti and Kortshagen (Phys. Rev. E 78, 046402, 2008), developed for the charging of dust particles.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Dynamic Formation of a Transient Jet from Arched Magnetized Laboratory Plasma

Abstract A laboratory plasma experiment was built to explore the eruptive behavior of arched magnetized plasmas with dimensionless parameters relevant to the Sun’s photosphere ( β ≈ 10 −3 , Lundquist number ≈10 4 , plasma radius/ion gyroradius ≈20, ion–neutral collision frequency ≫ion cyclotron frequency). Dynamic formation of a transient plasma jet was observed in the presence of the strapping magnetic field. The eruption leading to the jet is unintuitive because the arched plasma is both kink- and torus-stable. The jet structure erupts within a few Alfvén transit times from the formation of the arched plasma. Extensive measurements of plasma temperature, density, magnetic field, and flows are presented. In its early stages, the jet plasma flows away from the arch with supersonic speeds (Mach 1.5). This high-speed flow persists up to the resistive diffusion time in the arched plasma and is driven by large gradients in the magnetic and thermal pressures near the birthplace of jets. There are two distinct electric current channels within the jet, one consisting of outgoing electrons and another composed of electrons returning to the anode footpoint. Significant current density around the jet is a consequence of the diamagnetic current produced by a large thermal pressure gradient in the jet. Ion–neutral charge-exchange collisions provide an efficient mechanism to produce the cross-field current and control the dynamics of the complex current channels of the jet.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of Reactant Purity on Proton Exchange Membrane Fuel Cell Performance

NASA has set a goal to return to the Moon and to establish a sustained lunar presence. Many applicable lander and upperstage vehicle concepts utilize cryogenic H2 and O2 propellants. This propellant selection enables appealing potential mission concepts wherein electricity is generated by operating a fuel cell on residual H2 and O2 propellants. This concept depends on the capability of the fuel cell to utilize dry, propellant-grade reactants with concentrations of up to 30 percent He present. This study consists of the evaluation of a 12-cell non-flow-through proton exchange membrane fuel cell stack of 50 sq. cm active area with passive water removal. This stack was supplied with three levels of reactant purity: >99.999, 99.1, and 70 mol%, with the remainder made up of He. The reactant humidity and flow-through rate were also assessed as performance factors, and the fuel stack repeatedly supported a load profile with current densities up to 500 mA/sq. cm (25 A). The fuel cell performed consistently over the course of testing, with cell voltages decreasing approximately 50 mV at the maximum current density when supplied with reactants with 30 percent He present.

electrochemistry↗

Measurement of ion transport properties in ion exchange membranes for photoelectrochemical water splitting

Photoelectrochemical (PEC) water-splitting systems have the unique ability to produce renewable hydrogen directly from sunlight, independent of the electrical grid. These systems are therefore appealing technological options for resilient long-term energy storage. Ion selective membranes, such as monopolar and bipolar membranes, are a vital component of PEC water-splitting systems. These membranes allow for ionic conduction between the cathode and anode chambers, separation of products, and improved catalyst environments for reactions. In order to measure key properties and to study the performance of these ion exchange membranes, it is imperative to develop a robust testing protocol that can be used across the field. This paper introduces two standard electrochemical cells designed to directly measure ion transport properties in monopolar and bipolar membranes. The first electrochemical cell uses commercially available Pt disk electrodes to preform electrochemical impedance spectroscopy (EIS) and reliably measure through-plane conductivity of monopolar membranes. The second electrochemical cell uses four-point measurements with Luggin capillaries and a series of membrane configurations to perform current density-voltage and Faradaic efficiency (FE) measurements for water dissociation (WD) reactions on bipolar membranes. The cell designs and techniques laid out below allow for accurate measurement of ion transport parameters in ion exchange membranes, direct comparison of membranes being developed across the field, and in turn, greater advancements in ion exchange membranes and PEC water-splitting systems.

cation exchange membrane↗

Cation-Diffusive Carbon Interlayers Stabilize Na Metal and Double the Current in Na-S Redox-Flow Batteries for Grid-Scale Energy Storage

The sodium-sulfur nonaqueous redox-flow batteries (Na-S NARFBs) using earth-abundant elements are highly attractive due to the low material cost and improved energy density for grid-scale energy storage. However, the low current performance, poor Na0/Na+ redox kinetics, and Na dendrite growth pose severe challenges. We introduce cation-diffusive layers (CDLs): thin and Na+ affinitive interlayers at the Na anode that direct Na+ transport and stabilize Na deposition. Benchmarking three archetypal materials—carbon paper (CP), glass microfiber paper (GF), and foam—across Na-Na and Na-Cu, and Na-S cells identifies CP as the optimum. CP reduces symmetric cell overpotential by more than 70%, achieves 98% Na plating-stripping efficiency, and doubles the Na-S cell current density from 0.5 to 1.0 mA cm−2 without sacrificing capacity or efficiency. Ex situ electrochemical and SEM/XPS analysis, combined with molecular dynamics (MD) studies, reveal that electron-rich carbon fibers disperse supporting salt aggregates, enrich near-surface Na+ density, and create ion transport pathways for fast Na0/Na+ exchange while mitigating membrane degradation. Because of the ion-centric mechanism, CDLs can be generalized to other metal-anode designs. Further, this work establishes CDL design rules—cationic affinity and appropriate micro/nanostructure—as a simple, scalable route to high-current, durable metal-anode flow batteries.

Wu, Wenda [ORNL] (ORCID:000900033307687X)↗