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DOE OSTI2024

Interpenetrated Structures for Enhancing Ion Diffusion Kinetics in Electrochemical Energy Storage Devices

The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices (EESDs) by increasing surface area, thickness, and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity. However, conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients, limiting reaction kinetics. We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity. This free-standing device structure also avoids short-circuiting without needing a separator. The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion. Starting with a 3D-printed interpenetrated polymer substrate, we metallize it to make it conductive. This substrate has two individually addressable electrodes, allowing selective electrodeposition of energy storage materials. Using a Zn//MnO 2 battery as a model system, the interpenetrated device outperforms conventional separate electrode configurations, improving volumetric energy density by 221% and exhibiting a higher capacity retention rate of 49% compared to 35% at temperatures from 20 to 0 °C. Our study introduces a new EESD architecture applicable to Li-ion, Na-ion batteries, supercapacitors, etc.

25 ENERGY STORAGE↗

DOE OSTI2026

Influence of Nd(II) and Nd(III) Ions on the Speciation and Kinetic Dynamics of Radiolytic Transients in Molten LiCl-KCl Eutectic Salt Mixtures

In the pyrochemical reprocessing of used nuclear fuel, understanding the effects of ionizing radiation on the chemical behavior of fission products in molten chloride eutectic salt is crucial. Here, this study investigates the impact of radiation on the chemical and kinetic speciation of Nd ions in molten LiCl-KCl eutectic, which are challenging to separate due to their multivalent oxidation states and comproportionation reactions. Electron pulse radiolysis techniques were used to determine transient absorption spectra, chemical kinetics, and activation parameters for the reaction of Nd ions with the primary products of molten LiCl-KCl eutectic radiolysis: the solvated electron (e S - ) and dichlorine radical anion (Cl 2 •- ). Initially, Nd(III) reacted rapidly with e S - , forming Nd(II) with a second-order rate coefficient of k = (4.54 ± 0.07) × 10 10 M -1 s -1 at 673 K. The resulting Nd(II) ions then reacted slowly with Cl 2 •- , regenerating Nd(III) with an estimated rate of k = (1.72 ± 0.04) × 10 10 M -1 s -1 at 673 K. Additionally, the comproportionation reaction of Nd(III) and Nd(s) to form Nd(II) was monitored chemically and electrochemically. This work suggests that the comproportionation reaction of Nd(III) with Nd(s) to form Nd(II) is unstable in molten LiCl-KCl eutectic.

36 - MATERIALS SCIENCE↗

DOE OSTI2024

Complete resolution across the neodymium/samarium isotopic envelope with a liquid sampling‐atmospheric pressure glow discharge — Orbitrap mass spectrometer

Rationale Nd and Sm isotope ratios play an important role in geological dating and as nuclear forensic signatures; however, the overlap of the respective 144, 148, 150 Nd/Sm isobars requires prior separations to be performed before analysis on typical MS platforms. The work presented here overcomes these isobaric interferences using ultrahigh‐mass resolution to alleviate interference without prior chemical separations. Methods A liquid sampling‐atmospheric pressure glow discharge ion source was coupled to a standard, QExactive Focus Orbitrap mass spectrometer, providing a mass resolution of ~80 k. A Spectroswiss FTMS booster X2 data acquisition package was used to collect extended transients, providing much higher mass resolution; ~230 k and ~600 k are employed here for Nd and Sm isotopes. Results While the standard Orbitrap resolution is far greater than typical “atomic” MS platforms, it was insufficient to alleviate all isobars. The use of a resolution of ~230 k resulted in baseline separation across the entire isotopic envelope for both Nd and Sm. Isotope ratios obtained from Nd:Sm mixtures using high‐resolution were equivalent to those found for individual‐element solutions, while isotope ratios obtained at a resolution of ~80 k (standard for the OEM data system) showed large deviations. Conclusions Use of ultrahigh‐resolution is an attractive alternative to extensive chemical separations to alleviate severe isobaric interferences. Sufficient mass resolution greatly reduces/eliminates the need for sample manipulations (separations) before analysis while reducing costs and total analysis times.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Amorphous K–Co–Mo–S x Chalcogel: A Synergy of Surface Sorption and Ion-Exchange

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. We report the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K 2 CoMo 2 S 10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo 5+ 2 and Mo 4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co 2+ ions. The ionically bound K + ions remain in the percolating pores of the Co–Mo–S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO 2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO 2 2+ ] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Machine learning reveals key ion selectivity mechanisms in polymeric membranes with subnanometer pores

Designing single-species selective membranes for high-precision separations requires a fundamental understanding of the molecular interactions governing solute transport. Here, we comprehensively assess molecular-level features that influence the separation of 18 different anions by nanoporous cellulose acetate membranes. Our analysis identifies the limitations of bulk solvation characteristics to explain ion transport, highlighted by the poor correlation between hydration energy and the measured permselectivity (R 2 = 0.37). Entropy-enthalpy compensation, spanning 40 kilojoules per mole, leads to a free-energy barrier (ΔG‡) variation of only ~8 kilojoules per mole across all anions. We apply machine learning to elucidate descriptors for energetic barriers from a set of 126 collected features. Notably, electrostatic features account for 75% of the overall features used to describe ΔG‡, despite the relatively uncharged state of cellulose acetate. Our work presents an approach for studying ion transport across nanoporous membranes that could enable the design of ion-selective membranes.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Ion-Pair Reorganization Regulates Reactivity in Photoredox Catalysts

Cyclometalated and polypyridyl complexes of d6 metals are promising photoredox catalysts, using light to drive reactions with high kinetic or thermodynamic barriers via the generation of reactive radical intermediates. However, while tuning of their redox potentials, absorption energy, excited-state lifetime and quantum yield are well-known criteria for modifying activity, other factors could be important. Here we show that dynamic ion-pair reorganization controls the reactivity of a photoredox catalyst, [Ir[dF(CF3)ppy]2(dtbpy)]X. Time-resolved dielectric-loss experiments show how counter-ion identity influences excited-state charge distribution, evincing large differences in both the ground- and excited-state dipole moment depending on whether X is a small associating anion (PF6-) that forms a contact-ion pair versus a large one that either dissociates or forms a solvent-separated pair (BArF4-). These differences correlate with the reactivity of the photocatalyst toward both reductive and oxidative electron transfer, amounting to a 4-fold change in selectivity toward oxidation versus reduction. These results suggest that ion pairing could be an underappreciated factor that modulates reactivity in ionic photoredox catalysts.

catalysis↗

DOE OSTI2021

High-Current Light-Ion Cyclotron for Applications in Nuclear Security and Radioisotope Production

In this article, we propose the conceptual design, with supporting beam dynamics results, of a normal conducting, separated-sector cyclotron with a strong-focusing field gradient designed to accelerate light ions with a charge-to-mass ratio of 1/2 up to 15–20 MeV/u. The design can support a host of applications for therapy, radiobiology, material science, and instrumentation development. The light-ion species, which can include a mixed ion beam, can be dynamically chosen to provide a range of characteristic signals appropriate for specific material identification such as special nuclear materials. A conservative baseline concept is presented which has been optimized for radioisotope production of alpha emitters and theranostic radiopharmaceuticals. The modular design is also demonstrated to be scalable in gross physical parameters by a factor of 2–3, thereby reducing the size, weight, and power requirements (SWaP) and enabling near-term security applications.

07 ISOTOPE AND RADIATION SOURCES↗

NASA NTRS1981

Non-E x B ordered ion beams upstream of the earth's bow shock

The unexpected appearance of spin modulations in the fixed voltage electrostatic analyzer detectors on ISEE 1 and 2 has made it possible to study the plasma properties of the upstream ions in high time resolution. Using an isotropic flowing Maxwellian distribution to model the count rate modulations, estimates have been obtained of the local plasma temperature and three-dimensional flow velocity of the observed upstream ion population. It is found that in almost all of the observations of upstream particles there exist beam-like ions with temperatures in the range 5-80 eV. Their flow velocities cannot be ordered by E x B. This last point separates these observations from the previously reported reflected and diffuse populations of upstream ions. Mechanisms that can gyrophase bunch the ions reflected at the bow shock are discussed as a method of explaining the data.

Gurgiolo, C.↗

NASA NTRS2013

Multi-Pass Quadrupole Mass Analyzer

Analysis of the composition of planetary atmospheres is one of the most important and fundamental measurements in planetary robotic exploration. Quadrupole mass analyzers (QMAs) are the primary tool used to execute these investigations, but reductions in size of these instruments has sacrificed mass resolving power so that the best present-day QMA devices are still large, expensive, and do not deliver performance of laboratory instruments. An ultra-high-resolution QMA was developed to resolve N2 +/CO+ by trapping ions in a linear trap quadrupole filter. Because N2 and CO are resolved, gas chromatography columns used to separate species before analysis are eliminated, greatly simplifying gas analysis instrumentation. For highest performance, the ion trap mode is used. High-resolution (or narrow-band) mass selection is carried out in the central region, but near the DC electrodes at each end, RF/DC field settings are adjusted to allow broadband ion passage. This is to prevent ion loss during ion reflection at each end. Ions are created inside the trap so that low-energy particles are selected by low-voltage settings on the end electrodes. This is beneficial to good mass resolution since low-energy particles traverse many cycles of the RF filtering fields. Through Monte Carlo simulations, it is shown that ions are reflected at each end many tens of times, each time being sent back through the central section of the quadrupole where ultrahigh mass filtering is carried out. An analyzer was produced with electrical length orders of magnitude longer than its physical length. Since the selector fields are sized as in conventional devices, the loss of sensitivity inherent in miniaturizing quadrupole instruments is avoided. The no-loss, multi-pass QMA architecture will improve mass resolution of planetary QMA instruments while reducing demands on the RF electronics for high-voltage/high-frequency production since ion transit time is no longer limited to a single pass. The QMA-based instrument will thus give way to substantial reductions of the mass of flight instruments.

Prestage, John D.↗

DOE OSTI2024

Self-Assembled Bolaamphiphile-Based Organic Nanotubes as Efficient Cu(II) Ion Adsorbents

Self-assembled organic nanotubes (ONTs) have been actively examined for various applications such as chemical separations and catalysis owing to their well-defined tubular nanostructures with distinct chemical environments at the wall and internal/external surfaces. Adsorption of heavy metal ions onto ONTs plays an essential role in many of these applications, but it has rarely been assessed quantitatively. Herein, we investigated interactions between Cu 2+ and single-/quadruple-wall bolaamphiphile-based ONTs having inner carboxyl groups with different inner diameters, COOH-ONT 10nm and COOH-ONT 20nm . We first examined the effects of Cu 2+ on their nanotubular structures using SAXS, STEM, and AFM. COOH-ONT 10nm was stable in aqueous Cu 2+ solution in contrast to COOH-ONT 20nm owing to the presence of polyglycine-II-type hydrogen bonding networks within its wall. Subsequently, we studied the Cu 2+ adsorption behavior of COOH-ONT 10nm by monitoring the concentration of unbound Cu 2+ using linear sweep anodic stripping voltammetry. The Cu 2+ adsorption was quick, attributable to efficient Cu 2+ partitioning through the open ends of the ONT, followed by fast Cu 2+ diffusion in the uniform, relatively large nanochannel. More importantly, the Cu 2+ adsorption capacity and affinity of COOH-ONT 10nm were measured at different pH using the Langmuir adsorption model. The adsorption capacity was similar at the pH range examined, showing the participation of approximately 25% of the inner carboxyl groups in the adsorption. The adsorption affinity increased with pH, indicating the essential role of the deprotonated carboxyl groups in the Cu 2+ adsorption. Most interestingly, the Langmuir adsorption constant was significantly higher than those of previously reported synthetic adsorbents and planar monolayer based on carboxyl binding sites. The high Cu 2+ affinity of the ONT was attributable to the highly dense binding sites on the well-defined nanoscale concave structure of the inner channel. Furthermore, these results provide a valuable guideline to designing self-assembled nanomaterials for efficient chemical separations, detection, and catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Multi-scale boron penetration toward stabilizing nickel-rich cathode

Nickel-rich layered oxides LiNi x Co y Mn 1-x-y O 2 (x≥0.8) have been recognized as the preferred cathode materials to develop lithium-ion batteries with high energy density (>300Wh kg -1 ). However, the poor cycling stability and rate capability stemming from intergranular cracks and sluggish kinetics hinder their commercialization. To address such issues, a multi-scale boron penetration strategy is designed and applied on the polycrystalline LiNi 0.83 Co 0.11 Mn 0.06 O 2 particles that are pre-treated with pore construction. The lithium-ion conductive lithium borate in grain gaps functions as the grain binder that can bear the strain/stress from anisotropic contraction/expansion, and provides more pathways for lithium-ion diffusion. As a result, the intergranular cracks are ameliorated and the lithium-ion diffusion kinetics is improved. Moreover, the coating layer separates the sensitive cathode surface and electrolyte, helping to suppress the parasitic reactions and related gas evolution. In addition, the enhanced structural stability is acquired by strong B-O bonds with trace boron doping. As a result, the boron-modified sample with an optimized boron content of 0.5% (B5-NCM) exhibits a higher initial discharge capacity of 205.5mAh g -1 at 0.1C (1C=200mA g -1 ) and improved capacity retention of 81.7% after 100 cycles at 1C. Furthermore, the rate performance is distinctly enhanced by high lithium-ion conductive LBO (175.6mAh g -1 for B5-NCM and 154.6mAh g -1 for B0-NCM at 5C).

25 ENERGY STORAGE↗

NASA NTRS1987

Thermal ion perturbations observed in the vicinity of the Space Shuttle

Thermal ion characteristics in the vicinity of the Space Shuttle, derived from RF spectrometer measurements of the Plasma Diagnostic Package (PDP) flown aboard Spacelab 2, are discussed. During the Reaction Control System firings, short pulses of enhanced ion fluxes of NO(+), O2(+), and H2O(+) were detected in the near wake within and in near proximity to the open payload. During the release of the PDP as a free flying satellite, the spin modulation of the ion fluxes in the ion spectrometer indicated the presence of plasma streams of O(+) and H2O(+) which were separated in direction by as much as 77 deg. It is concluded that the presence of contaminant NO and O2(+) ions makes the near environment of the Shuttle an unsuitable place for obtaining accurate ambient ion concentration measurements.

Grebowsky, J. M.↗

DOE OSTI2023

Status of CHIP-TRAP: The Central Michigan University High-Precision Penning Trap

Precise and accurate atomic mass data provide crucial information for applications in a wide range of fields in physics and beyond, including astrophysics, nuclear structure, particle and neutrino physics, fundamental symmetries, chemistry, and metrology. The most precise atomic mass measurements are performed on charged particles confined in a Penning trap. Here, we describe the development, status, and outlook of CHIP-TRAP: the Central Michigan University high-precision Penning trap. CHIP-TRAP aims to perform ultra-high precision (~1 part in 10 11 fractional precision) mass measurements on stable and long-lived isotopes produced with external ion sources and transported to the Penning traps. Along the way, ions of a particular m/q are selected with a multi-reflection time-of-flight mass separator (MR-TOF-MS), with further filtering performed in a cylindrical capture trap before the ions are transported to a pair of hyperbolic measurement traps. In this paper, we report on the design and status of CHIP-TRAP and present results from the commissioning of the ion sources, MR-TOF-MS, and capture trap. We also provide an outlook on the continued development and commissioning of CHIP-TRAP.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

NASA NTRS1993

Ionospheric plasma flow about a system of electrically biased flat plates

The steady state interaction of two electrically biased parallel plates immersed in a flowing plasma characteristic of low earth orbit is studied numerically. Fluid equations are developed to describe the motion of the cold positively charged plasma ions, and are solved using finite-differences in two dimensions on a Cartesian grid. The behavior of the plasma electrons is assumed to be described by the Maxwell-Boltzmann distribution. Results are compared to an analytical and a particle simulation technique for a simplified flow geometry consisting of a single semi-infinite negatively biased plate. Comparison of the extent of the electrical disturbance into the flowing plasma and the magnitude of the current collected by the plate is very good. The interaction of two equally biased parallel plates is studied as a function of applied potential. The separation distance at which the current collected by either plate decreases by five and twenty percent is determined as a function of applied potential. The percent decreases were based on a non-interacting case. The decrease in overall current is caused by a decrease in ionic density in the region between the plates. As the separation between the plates decreases, the plates collect the ions at a faster rate than they are supplied to the middle region by the oncoming plasma flow. The docking of spacecraft in orbit is simulated by moving two plates of unequal potential toward one another in a quasi-static manner. One plate is held at a large negative potential while the other floats electrically in the resulting potential field. It is found that the floating plate does not charge continuously negative as it approaches the other more negatively biased plate. Instead, it charges more and then less negative as ionic current decreases and then increases respectively upon approach. When the two plates come into contact, it is expected that the electrically floating plate will charge rapidly negative to a potential near that of the other plate.

Herr, Joel L.↗

DOE OSTI2024

Interpenetrating 3D Electrodes for High-Rate Alkaline Water Splitting

Mass transfer is critical for the reaction kinetics and efficiency of alkaline water splitting (AWS). For AWS to operate at high current densities (hundreds of mA/cm 2 ), the device architecture must ensure a large catalytic surface area, rapid ion diffusion, and minimal solution and charge transfer resistances. Effective electrodes should also facilitate gas bubble detachment and release. 3D-printed electrodes have shown promise, but stacking them increases the ion diffusion length and solution resistance. Here we demonstrate a new device architecture with interpenetrating gyroid electrodes, providing a large ion-accessible surface area and gas diffusion channels. This design significantly reduces the interelectrode distance, lowering ion diffusion length and solution resistance. Simulations show faster ion diffusion and higher current density in the interpenetrating configuration compared with separate electrodes. This improved performance, especially at low temperatures and high current densities, highlights a promising strategy for enhancing AWS and other electrochemical systems limited by slow ion diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

A second order yield-temperature relation for accurate inference of burn-averaged quantities in multi-species plasmas

Measured yields and ion temperatures inferred from the fusion product energy spectra can be used as metrics for the performance of an ICF implosion. This can be to infer species separation, thermal decoupling, flows or other effects that can cause the inferred ion temperatures to deviate from the true underlying thermal temperature and the yield ratio to deviate from the expected value. Direct inference of the impact of these effects on observed temperatures and yields can be difficult to uncover due to underlying dependence on the shape and time evolution of the temperature and density proles of the fusing plasma. Due to differences in the temperature dependence of the reactivities, different fusion products are emitted from different regions and times within the implosion. In order to properly account for this, a second order analytic expression relating the apparent temperatures and yield ratios is developed. This expression can be coupled to models of yield and/or temperature altering effects to infer their burn-averaged impact on an implosion. The second order expression shows significant improvement over lower order expressions in synthetic data studies. Demonstrations of its applications to synthetic data coupled with models of ion thermal decoupling and radial flows are presented. In the case of thermal decoupling both first and second order expressions show reasonable levels of accuracy. To consistently infer the amplitude of radial flow with <10% error the second order equation is required.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

NASA NTRS1995

Progress Report on the Improved Linear Ion Trap Physics Package

This article describes the first operational results from the extended linear ion trap frequency standard now being developed at JPL. This new design separates the state selection/interrogation region from the more critical microwave resonance region where the multiplied local oscillator (LO) signal is compared to the stable atomic transition. Hg+ ions have been trapped, shuttled back and forth between the resonance and state selection traps. In addition, microwave transitions between the Hg+ clock levels have been driven in the resonance trap and detected in the state selection trap.

Linear Ion Trap↗

DOE OSTI2022

Structural basis for inhibition of the Cation-chloride cotransporter $\mathrm{NKCC1}$ by the diuretic drug bumetanide

Cation-chloride cotransporters (CCCs) NKCC1 and NKCC2 catalyze electroneutral symport of 1 Na + , 1K + , and 2 Cl - across cell membranes. NKCC1 mediates trans-epithelial Cl - secretion and regulates excitability of some neurons and NKCC2 is critical to renal salt reabsorption. Both transporters are inhibited by the so-called loop diuretics including bumetanide, and these drugs are a mainstay for treating edema and hypertension. Here, our single-particle electron cryo-microscopy structures supported by functional studies reveal an outward-facing conformation of NKCC1, showing bumetanide wedged into a pocket in the extracellular ion translocation pathway. Based on these and the previously published inward-facing structures, we define the translocation pathway and the conformational changes necessary for ion translocation. We also identify an NKCC1 dimer with separated transmembrane domains and extensive transmembrane and C-terminal domain interactions. We further define an N-terminal phosphoregulatory domain that interacts with the C-terminal domain, suggesting a mechanism whereby (de)phosphorylation regulates NKCC1 by tuning the strength of this domain association.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗