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At least 37 records · Page 2

Locally Confined Polysulfide-Reactive Electrolytes for Shuttle-Free Sodium–Sulfur Batteries

Sodium-sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfides dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte-electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfides solvation and stabilizing sodium interfaces. Here, we present a locally-confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode-electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium-metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (> 3 mg S cm −2 with commercial carbon host and 70 wt% sulfur content), which afford 710 mA h g −1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. Furthermore, this work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.

25 ENERGY STORAGE↗

Mass Spectrometric Determination of Site-Specific O -Acetylation in Rhamnogalacturonan I Oligomers

O-acetylation, a common modification in rhamnogalacturonan I (RG-I), is critical for various biological processes, including plant growth, stress responses, and pathogen defense. Precise determination of the degree and specific positions of acetylation is therefore essential. To date, nuclear magnetic resonance (NMR) and tandem mass spectrometry have been employed to identify O-acetyl positions in pectin oligosaccharides. Although NMR is effective, it requires pure, high-concentration samples. Tandem mass spectrometry (MS), which uses smaller sample amounts, faces challenges due to O-acetyl migration between monosaccharide positions. The multiple steps in pectin sample analysis can further promote O-acetyl migration, especially near free hydroxyl groups. Moreover, during tandem MS, O-acetyl groups may detach, complicating the accurate tracking. This study presents an approach to lock O-acetyl groups by introducing trideuteroacetyl and propionyl substituents onto free hydroxyls of RG-I or partially acetylated RG-I. By combining matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) MS and electrospray ionization (ESI) MS with MS/MS or tandem mass spectrometry (MSn), we devised a way to determine the monosaccharide sequence in the oligomer and the precise positions of O-acetyl groups in partially acetylated RG-I. This method enables the study of the regiospecificity of recombinant pectin O-acetyltransferases and can be applied to other oligosaccharides to determine acyl positions.

O-acetylation↗

Hydrotrope-enabled high concentration aqueous electrolytes for reversible and sustainable iron metal anodes

Iron metal-based energy storage devices hold great potential in stationary grid-scale sustainable energy due to the high theoretical specific capacity, ultralow cost, and abundance of iron. However, their practical deployment is limited by the poor reversibility of iron plating and stripping, as well as competitive hydrogen evolution. Here we introduce the concept of hydrotropy into iron electrolytes by developing an environmentally friendly and cost-effective high-concentration ferrous sulfate electrolyte using urea as a hydrotropic agent. The designed electrolyte increases the Coulombic efficiency of iron metal electrodes to approximately 96.5%, compared with ~84.6% for the dilute electrolyte. Molecular dynamics simulations and Raman spectroscopy illustrate that urea regulates the competitive coordination of anions and urea in the iron solvation sheath, while reconstructing the hydrogen-bond network in free water molecules. This reduces the activity of both solvated and free water, thereby alleviating hydrogen evolution. Moreover, the coordinated anions and urea molecules facilitate the in-situ formation of an organic-inorganic hybrid protective layer on the metallic iron, establishing a physical barrier against water and promoting homogeneous interfacial reactions. This work demonstrates an appealing opportunity to design cost-effective and high-performance electrolytes and propels the practical application of iron metal-based energy storage devices.

Feng, Guangxia [Stanford Univ., CA (United States)↗

Quantitative insights for diagnosing performance bottlenecks in lithium–sulfur batteries

Lithium–sulfur (Li–S) batteries hold significant promise for electric vehicles and aviation due to their high energy density and cost-effectiveness. However, understanding the root causes of performance degradation remains a formidable challenge, as the interplay of multiple factors obscures key failure mechanisms. A major limitation has been the inability to quantify soluble sulfur species within practical detection limits accurately and to correlate electrochemical processes with associated physical inventory changes. Here, we introduce the high-performance liquid chromatography-ultraviolet spectroscopy and gas chromatography sequential characterization (HUGS) toolkit, capable of precisely quantifying seven distinct sulfur and polysulfide species at concentrations as low as 40 ppb. HUGS has been successfully applied to practical coin and pouch cells without requiring cell modification. Furthermore, our self-developed software, Dr HUGS, enhanced the data analysis speed by over 30 times, enabling multi-source data integration and delivering comprehensive analysis results within minutes. Using HUGS, we identify significant capacity losses from inactive lithium and sulfur during initial cycles and sulfide-rich solid–electrolyte interphase (SEI) formation on the anode during later cycles. Notably, our findings reveal that soluble polysulfides have minimal contributions to capacity loss, challenging long-standing assumptions. Moreover, HUGS demonstrates that constant-pressure setups in Li–S pouch cells improve compositional uniformity compared to constant-gap configurations. For sulfurized polyacrylonitrile (SPAN) cathodes, unique issues such as non-sulfide SEI formation and lithium pulverization are observed, which can be mitigated through localized high-concentration electrolytes to enhance lithium inventory retention. By enabling precise quantification of critical inventory components, HUGS provides transformative insights into failure mechanisms across various electrolytes and cathode chemistries, guiding rational design strategies for next-generation energy storage systems.

25 ENERGY STORAGE↗

Vertical Characterization of Flow and Contaminant Concentration in New Hanford Extraction Wells

Effective groundwater remediation should focus on high-concentration, low-permeability zones within the aquifer, as these areas often present significant challenges to contaminant removal. Characterizing the vertical distribution of contamination in an aquifer is therefore critical for optimizing and monitoring pump-and-treat (P&T) systems to meet target cleanup timelines. Flow patterns driven by hydraulic gradients and variations in permeability are described to provide insight into contaminant mass removal from long-screened wells. The objective of this multi-phase work is to provide actionable recommendations for improving remedy performance monitoring and P&T operations, which ongoing evaluations will address. This report summarizes the preliminary results of vertical flow and contaminant distribution monitoring in new extraction wells at the Hanford Site.

54 ENVIRONMENTAL SCIENCES↗

Solvated Ionic Liquid-based Electrolytes: Experimental Characterization, Atomistic Modeling and Applications in Energy Storage

This study aimed on understanding the molecular structure and transport mechanisms of high-concentration lithium electrolytes, with a particular focus on solvate ionic liquids (SILs) based on glyme solvents, for use in next-generation, high-voltage energy storage systems. The hypothesis is that the composition of the solvents in these electrolytes can be designed and adjusted to control cation solvation, enabling charge transport via an ion-hopping mechanism. This mechanism resembles Grotthuss conduction of protons in water and is independent of electrolyte viscosity. The experimental studies employed linear and nonlinear infrared spectroscopy (FTIR and 2D IR), electrochemical measurements, and vibrational probes.

25 ENERGY STORAGE↗

Silicon solar photovoltaic power stations

Modular design of components and arrays, cost estimates for modules and support structures, and cost/performance analysis of a central solar photovoltaic power plant are discussed. Costs of collector/reflector arrays are judged the dominant element in the total capital investment. High-concentration solar tracking arrays are recommended as the most economic means for producing solar photovoltaic energy when solar cells costs are high ($500 per kW generated). Capital costs for power conditioning subsystem components are itemized and system busbar energy costs are discussed at length.

Chowaniec, C. R.↗

The growth of zeolites A, X and mordenite in space

Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

Sacco, Albert, Jr.↗

The stellar population in the core of M15

The inner core of the globular cluster M15 within approximately 2 sec of the geometrical center has been explored with high-resolution images taken through several broad-band UV filter with the Faint Object Camera (FOC) on board the Hubble Space Telescope (HST). Approximately 210 stars in this region down to a 5 sigma detection limit of m(sub 220) = 21.5 were reliably identified and located on a UV - U color magnitude diagram for the first time. A majority of stars (about 70% of the total) observed this way lie above the expected main-sequence turn-off of this cluster and below the sparsely populated horizontal branch. The extension of the main sequence above the turn-off separates this population in two roughly equal components situated to the right and left of this line. Most of the former must be classical blue stragglers while the rest belong to a new, as yet unidentified, population of very blue stars. Possibilities include, but are not restricted to, well-mixed single stars, subdwarfs, and helium white dwarfs. Similar objects are also found just outside the core out to approximately 6 sec from the center, but the brighter, presumably more massive ones, are sharply confined to the core itself. The measured excess of bright blue stars and the relative deficiency of bright red giants in the core are consistent with the blue inward color gradient measured from the ground and imply that dynamical evolution can significantly affect the stellar population in the very dense central regions of a high-concentration globular cluster like M15.

De Marchi, Guido↗

On treatments of fetch and stability sensitivity in large-area estimates of sensible heat flux over sea ice

Bulk transfer coefficients estimated as a function of atmospheric stability and sea-ice lead width are combined with Arctic meteorological observations and ice thickness data to calculate the sensitivity of turbulent flux estimates to changes in lead width, wind speed, air temperature, and ice thickness for a high-concentration ice pack. These results are considered in terms of bulk transfer parameterizations that use a fixed transfer coefficient r that address atmospheric stability only. On the basis of the fetch-sensitive parameterizations considered here, differences in lead width for widths up to about 200 m can exert a substantial influence on sensible heat transfer coefficients and heat flux from leads under typical Arctic conditions. Fluxes from an open water lead decrease by 34% if fetch increases from 10 m to 100 m. This effect is greatest for open water leads, decreases considerably as leads refreeze, and is negligible for ice thicker than about 0.3 m. If open or newly refrozen leads make up 2% of the ice cover, than an increase in mean fetch from 10 m to 100 m yields a decrease of about 2 W/sq m in areally averaged flux from the ice pack. Calculations using observed and theoretical lead width distributions suggest that parameterizing lead widths in a sea ice model can be done effectively using a single, representative lead width rather than requiring a full distribution of widths. When coupled to the lowest atmospheric boundary layer using a bulk similarity theory model, this sensitivity of heat transfer to fetch results in substantially higher near-surface air temperatures over narrow leads, with equilibrium air temperatures decreasing by about 50% as fetch increases from 10 to 100 m.

Maslanik, J. A.↗

Parameterization and scaling of arctic ice conditions in the context of ice-atmospheric processes

The goals of this project are to observe how the open water/thin ice fraction in a high-concentration ice pack responds to different short-period atmospheric forcings, and how this response is represented in different scales of observation. The objectives can be summarized as follows: determine the feasibility and accuracy of ice concentration and ice typing by ERS-1 SAR backscatter data, and whether SAR data might be used to calibrate concentration estimates from optical and massive-microwave sensors; investigate methods to integrate SAR data with other satellite data for turbulent heat flux parameterization at the ocean/atmosphere interface; determine how the development and evolution of open water/thin ice areas within the interior ice pack vary under different atmospheric synoptic regimes; compare how open-water/thin ice fractions estimated from large-area divergence measurements differ from fractions determined by summing localized openings in the pack; relate these questions of scale and process to methods of observation, modeling, and averaging over time and space.

Barry, R. G.↗

Modeling of Macroscopic/Microscopic Transport and Growth Phenomena in Zeolite Crystal Solutions Under Microgravity Conditions

Crystals grown from liquid solutions have important industrial applications. Zeolites, for instance, a class of crystalline aluminosilicate materials, form the backbone of the chemical process industry worldwide, as they are used as adsorbents and catalysts. Many of the phenomena associated with crystal growth processes are not well understood due to complex microscopic and macroscopic interactions. Microgravity could help elucidate these phenomena and allow the control of defect locations, concentration, as well as size of crystals. Microgravity in an orbiting spacecraft could help isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation. In addition, crystals will stay essentially suspended in the nutrient pool under a diffusion-limited growth condition. This is expected to promote larger crystals by allowing a longer residence time in a high-concentration nutrient field. Among other factors, the crystal size distribution depends on the nucleation rate and crystallization. These two are also related to the "gel" polymerization/depolymerization rate. Macroscopic bulk mass and flow transport and especially gravity, force the crystals down to the bottom of the reactor, thus forming a sedimentation layer. In this layer, the growth rate of the crystals slows down as crystals compete for a limited amount of nutrients. The macroscopic transport phenomena under certain conditions can, however, enhance the nutrient supply and therefore, accelerate crystal growth. Several zeolite experiments have been performed in space with mixed results. The results from our laboratory have indicated an enhancement in size of 30 to 70 percent compared to the best ground based controls, and a reduction of lattice defects in many of the space grown crystals. Such experiments are difficult to interpret, and cannot be easily used to derive empirical or other laws since many physical parameters are simultaneously involved in the process. At the same time, however, there is increased urgency to develop such an understanding in order to more accurately quantify the process. In order to better understand the results obtained from our prior space experiments, and design future experiments, a detailed fluid dynamic model simulating the crystal growth mechanism is required. This will not only add to the fundamental knowledge on the crystallization of zeolites, but also be useful in predicting the limits of size and growth of these important industrial materials. Our objective is to develop macro/microscopic theoretical and computational models to study the effect of transport phenomena in the growth of crystals grown in solutions. Our effort has concentrated so far in the development of separate macroscopic and microscopic models. The major highlights of our accomplishments are described.

Gatsonis, Nikos A.↗

Upper-Stage Flight Experiment

For propulsion applications that require that the propellants are storable for long periods, have a high density impulse, and are environmentally clean and non-toxic, the best choice is a combination of high-concentration hydrogen peroxide (High Test Peroxide, or HTP) and a liquid hydrocarbon (LHC) fuel. The HTP/LHC combination is suitable for low-cost launch vehicles, space taxi and space maneuvering vehicles, and kick stages. Orbital Sciences Corporation is under contract with the NASA Marshall Space Flight Center in cooperation with the Air Force Research Lab to design, develop and demonstrate a new low-cost liquid upper stage based on HTP and JP-8. The Upper Stage Flight Experiment (USFE) focuses on key technologies necessary to demonstrate the operation of an inherently simple propulsion system with an innovative, state-of-the-art structure. Two key low-cost vehicle elements will be demonstrated - a 10,000 lbf thrust engine and an integrated composite tank structure. The suborbital flight test of the USFE is scheduled for 2001. Preceding the flight tests are two major series of ground tests at NASA Stennis Space Center and a subscale tank development program to identify compatible composite materials and to verify their compatibility over long periods of time. The ground tests include a thrust chamber development test series and an integrated stage test. This paper summarizes the results from the first phase of the thrust chamber development tests and the results to date from the tank material compatibility tests. Engine and tank configurations that meet the goals of the program are described.

Anderson, W. E.↗

Crystal Growth Using MEPHISTO

The shuttle flight experiment "In Situ Monitoring of Crystal Growth Using MEPHISTO" was accomplished during STS-87 as part of the fourth flight of the United States Microgravity Payload (USMP-4), which was flown from November 19 to December 5, 1997. The data returned from that flight are just now beginning to yield quantitative results. This project is an international collaboration: the furnace system known as MEPHISTO was built in France by CNES (French National Space Agency) and CEA (French Atomic Energy Commission); the principal investigator, Prof. Reza Abbaschian, is from the University of Florida at Gainesville; and numerical and analytical modeling support includes collaborators from the University of New South Wales, Australia, the University of Wisconsin at Milwaukee, the National Institute of Standards and Technology, and the NASA Lewis Research Center. MEPHISTO is a French acronym that translates into English as Materials for the Study of Interesting Phenomena of Solidification on Earth and in Orbit. Since this was the fourth flight of the MEPHISTO furnace, the experiment is referred to as MEPHISTO-4. MEPHISTO-4 was a directional solidification experiment that studied the liquid-to-solid transformation of bismuth alloyed with tin. Directional solidification is a freezing technique common to the processing of the electronic materials used in integrated circuits and detectors, such as silicon and germanium. When liquids are frozen on Earth, they must be cooled. The cooling causes stirring because of density variations in the liquid. This stirring, known as natural convection, influences the quality of the resulting solid. During freezing, regions of high and low concentrations of tin are created. This introduces another important phenomenon: diffusion, or the movement by molecular action of matter from regions of high concentration to regions of lower concentration. In MEPHISTO-4, it is tin that diffuses from the high-concentration region in front of the solid-liquid interface to more distant low-concentration regions.

deGroh, Henry C., III↗

Hazard Assessment of Personal Protective Clothing for Hydrogen Peroxide Service

Selection of personal protective equipment (PPE) for hydrogen peroxide service is an important part of the hazard assessment process. But because drip testing of chemical protective clothing for hydrogen peroxide service has not been reported for about 40 years, it is of great interest to test new protective clothing materials with new, high-concentration hydrogen peroxide following similar procedures. The suitability of PPE for hydrogen peroxide service is in part determined by observations made when hydrogen peroxide is dripped onto swatches of protective clothing material. Protective clothing material was tested as received, in soiled condition, and in grossly soiled condition. Materials were soiled by pretreating the material with potassium permanganate (KMnO4) solution then drying to promote a reaction. Materials were grossly soiled with solid KMnO4 to greatly promote reaction. Observations of results including visual changes to the hydrogen peroxide and materials, times to ignition, and self-extinguishing characteristics of the materials are reported.

Greene, Ben↗

Using a delta-doped CCD to determine the energy of a low-energy particle

The back surface of a thinned charged-coupled device (CCD) is treated to eliminate the backside potential well that appears in a conventional thinned CCD during backside illumination. The backside of the CCD includes a delta layer of high-concentration dopant confined to less than one monolayer of the crystal semiconductor. The thinned, delta-doped CCD is used to determine the energy of a very low-energy particle that penetrates less than 1.0 nm into the CCD, such as a proton having energy less than 10 keV.

Nikzad, Shouleh↗

Delta-doped CCD's as low-energy particle detectors and imagers

The back surface of a thinned charged-coupled device (CCD) is treated to eliminate the backside potential well that appears in a conventional thinned CCD during backside illumination. The backside of the CCD includes a delta layer of high-concentration dopant confined to less than one monolayer of the crystal semiconductor. The thinned, delta-doped CCD is used to detect very low-energy particles that penetrate less than 1.0 nm into the CCD, including electrons having energies less than 1000 eV and protons having energies less than 10 keV.

Nikzad, Shouleh↗

Method for Reduction of Silver Biocide Plating on Metal Surfaces

Silver ions in aqueous solutions (0.05 to 1 ppm) are used for microbial control in water systems. The silver ions remain in solution when stored in plastic containers, but the concentration rapidly decreases to non-biocidal levels when stored in metal containers. The silver deposits onto the surface and is reduced to non-biocidal silver metal when it contacts less noble metal surfaces, including stainless steel, titanium, and nickel-based alloys. Five methods of treatment of contact metal surfaces to deter silver deposition and reduction are proposed: (1) High-temperature oxidation of the metal surface; (2) High-concentration silver solution pre-treatment; (3) Silver plating; (4) Teflon coat by vapor deposition (titanium only); and (5) A combination of methods (1) and (2), which proved to be the best method for the nickel-based alloy application. The mechanism associated with surface treatments (1), (2), and (5) is thought to be the development of a less active oxide layer that deters ionic silver deposition. Mechanism (3) is an attempt to develop an equilibrium ionic silver concentration via dissolution of metallic silver. Mechanism (4) provides a non-reactive barrier to deter ionic silver plating. Development testing has shown that ionic silver in aqueous solution was maintained at essentially the same level of addition (0.4 ppm) for up to 15 months with method (5) (a combination of methods (1) and (2)), before the test was discontinued for nickel-based alloys. Method (1) resulted in the maintenance of a biocidal level (approximately 0.05 ppm) for up to 10 months before that test was discontinued for nickel-based alloys. Methods (1) and (2) used separately were able to maintain ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for stainless steel alloys. Method (3) was only utilized for titanium alloys, and was successful at maintaining ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for simple flat geometries, but not for geometries that are difficult to Teflon coat.

Steele, John↗