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At least 1,783 records · Page 99
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Electrochemical and Chemical Reactivities of Titanium Oxide-Based Materials with a Chloroaluminate Ionic Liquid Electrolyte for Aluminum Batteries

Here, by selecting three different types of electrode materials, we intended to better understand the Al 3+ intercalation chemistry of titanium oxide-based frameworks with an acidic chloroaluminate electrolyte. In agreement with previous reports, we confirmed that the native interstitial sites of anatase TiO 2 are less prone to accommodate Al 3 + than Li + or Na + ions, while introducing cationic vacancies largely increases the electrochemical storage capacity. Upon the first cycle, the highest reversible capacity, up to 277 mAh/g, was obtained for a hydrated layered structure featuring cationic vacancies. Total scattering data showed that the insertion of Al 3+ ions induced a strong distortion of the framework. In addition, combined 27 Al MAS NMR and DFT calculations revealed that in oxy-hydroxylated vacant sites, the coordination mode of Al 3+ ions depends on the arrangement of anions around vacancies inducing the occurrence of 4-, 5-, and 6-fold coordination modes. Further cycling experiments revealed a progressive capacity fading for all electrode materials. Using cyclic voltammetry on the used electrolyte, we evidenced that a partial dissolution has occurred, which is more pronounced for the layered hydrate compound, and that solubilized species are electrochemically active, giving rise to specific signatures in both CVs and galvanostatic experiments. Raman spectroscopy enabled us to characterize these species, which are derived from the Ti-Cl system. The solubilized species, however, eventually precipitated, as shown by a purple deposit observed on the separator and tentatively assigned to TiCl 3 , known to be insoluble in this medium. By providing further information on the Al 3+ intercalation chemistry and a better understanding of the electrochemical and chemical reactivities of electrode materials, this work will enable progress to be made in the development of aluminum-ion batteries.

Al3+-ion insertion chemistry↗
DOE OSTI2021

Bioresorbable Primary Battery Anodes Built on Core–Double-Shell Zinc Microparticle Networks

Bioresorbable implantable electronics require power sources that are also bioresorbable with controllable electrical output and lifetime. In this paper, we report a bioresorbable zinc primary battery anode filament based on a zinc microparticle (MP) network coated with chitosan and Al 2 O 3 double shells. When discharged in 0.9% NaCl saline, a Zn MP filament with a 0.17 × 2 mm 2 cross-sectional area exhibited a stable voltage output of 0.55 V at a current of 0.01 mA. Covered by chitosan and Al 2 O 3 double shells, the zinc MP filament exhibited a directional dissolution behavior with a tunable lifetime approximately linear to its length. A stable 200 h discharging time was achieved with a 15 mm Zn MP filament. The maximum output power was found to be 12 μW at 0.03 mA for one filament. The linearity relationship between the current output and the filament cross-sectional area suggested a facile strategy to raise the power output at constant discharging voltage. The filaments could also be connected in series and in parallel to boost its overall voltage and current output, demonstrating their excellent integration capability. Furthermore, this work presents a promising pathway toward bioresorbable transient batteries with controllable lifetime and power output, demonstrating a great potential for powering transient implantable biomedical devices.

25 ENERGY STORAGE↗
DOE OSTI2021

Replacement of Calcium Carbonate Polymorphs by Cerussite

Calcium carbonate (CaCO 3 ) polymorphs, calcite, aragonite, and vaterite, serve as a major sink to retain various metal ions in natural and engineered systems. Here, we visualize the systematic trends in reactivities of calcite, vaterite, and aragonite to Pb 2+ dissolved in acidic aqueous solutions using in situ optical microscopy combined with ex situ scanning electron and transmission X-ray microscopies. All three polymorphs undergo pseudomorphic replacement by cerussite (PbCO 3 ) but with distinct differences in the evolution of their morphologies. The replacement of calcite and aragonite occurs through the formation of a pseudomorphic cerussite shell (typically 5–10 μm thick) followed by a slower inward propagation of reaction fronts through a thin solution gap (~0.1 μm wide) between the shell and the CaCO 3 substrate. The replacement of vaterite is characterized by the formation of a thinner cerussite shell (≤1 μm thick) and a larger cavity between the shell and the host mineral. These systematic differences in cerussite morphology for different CaCO 3 polymorphs are explained by the relative dissolution and precipitation rates of the reactant and product minerals, coupled with the role of ion transport through the cerussite shells. We also find that the replacement of calcite by cerussite is the slowest when all three polymorphs coexisted. Furthermore, our results provide mechanistic insights into the growth mode of cerussite on dissolving calcium carbonate and demonstrate these CaCO 3 polymorphs as promising substrate materials for removal and recycling of Pb from acidic polluted water and industrial effluents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Emergent Behavior at the Calcite–Water Interface during Reactive Transport in a Simple Microfluidic Channel

Geochemical reactive transport processes in natural mineral-fluid systems may produce a wide array of emergent phenomena that are difficult to predict from basic principles and to reproduce in model systems. In this study, we present experimental results obtained from a simple microfluidic system with which we explored the consequences of reacting the calcite (104) cleavage surface with an acidic Pb-bearing solution (pH = 3.5, [Pb] total = 5 mM) as a function of flow rate. This system is relevant to passive remediation systems for Pb-rich acid mine drainage. We observed periodic banding in the amounts of Pb sorption at flow velocities ≥ 926 μm s -1 , where the band spacing was spatially correlated with the amount of calcite dissolution and the development of micropyramidal topography on the calcite (104) surface. The equivalent coverage of Pb deposited in these Pb-rich bands was at least several monolayers per unit cell, yet there was no evidence for precipitation of any secondary Pb phase implying incorporation of Pb within the near-surface calcite lattice. We also observed spatial variations in nucleation and growth of euhedral secondary Pb-carbonate minerals hydrocerusite and cerussite at flow rates ≤ 278 μm s -1 ,. These findings demonstrate potential for exploiting the rich phenomenology afforded by the interplay among transport phenomena and chemical kinetics in experimental systems designed to yield deeper insights into geochemical self-organization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reducing Pb and Cl Mobility in Waste-to-Energy Fly Ashes via Chlorellestadite Formation

Sustainably sourced development minerals are vital to meeting the demand for low-carbon construction materials. A potential waste material that can be a low-carbon construction material for cementitious systems is waste-to-energy fly ash (WTE ash), a by-product of waste incineration. WTE ash contains chloride-bearing species and heavy metals, which can promote steel reinforcement corrosion and present long-term leaching risks. Here, we present a new multi-step ash treatment protocol involving dissolution and heating to transform the non-readily removable chlorides in WTE ash to Chlorellestadite (Ca 10 (SiO 4 ) 3 (SO 4 ) 3 Cl 2 ). Our results suggest that this transformation significantly reduces chloride release from WTE ash in an alkaline cement-like environment by over two orders of magnitude, from 1500 mg/l to less than 10 mg/l. This transformation also significantly reduces Pb mobility after treatment (from > 5 mg/l to < 0.5 mg/l), likely caused by the crystallo-chemical incorporation of Pb in Chlorellestadite. In contrast to the existing ash treatment methods, the proposed ash treatment protocol minimizes heavy metals volatilization while simultaneously reducing Pb mobility and chloride release through Chlorellestadite formation. Furthermore, these findings overcome limitations preventing the commercial use of WTE ash and thus opening up pathways towards a circular economy.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover

The formation of metallic lithium microstructures in the form of dendrites or mosses at the surface of anode electrodes (e.g., lithium metal, graphite, and silicon) leads to rapid capacity fade and poses grave safety risks in rechargeable lithium batteries. In this work, we present here a direct, relative quantitative analysis of lithium deposition on graphite anodes in pouch cells under normal operating conditions, paired with a model cathode material, the layered nickel-rich oxide LiNi 0.61 Co 0.12 Mn 0.27 O 2 , over the course of 3000 charge-discharge cycles. Secondary-ion mass spectrometry chemically dissects the solid-electrolyte interphase (SEI) on extensively cycled graphite with virtually atomic depth resolution and reveals substantial growth of Li-metal deposits. With the absence of apparent kinetic (e.g., fast charging) or stoichiometric restraints (e.g., overcharge) during cycling, we show lithium deposition on graphite is triggered by certain transition-metal ions (manganese in particular) dissolved from the cathode in a disrupted SEI. This insidious effect is found to initiate at a very early stage of cell operation (<200 cycles) and can be effectively inhibited by substituting a small amount of aluminum (~1 mol %) in the cathode, resulting in much reduced transition-metal dissolution and drastically improved cyclability. In conclusion, our results may also be applicable to studying the unstable electrodeposition of lithium on other substrates, including Li metal.

25 ENERGY STORAGE↗
DOE OSTI2013

Modifications of Carbonate Fracture Hydrodynamic Properties by CO 2 -Acidified Brine Flow

Acidic reactive flow in fractures is relevant in subsurface activities such as CO{sub 2} geological storage and hydraulic fracturing. Understanding reaction-induced changes in fracture hydrodynamic properties is essential for predicting subsurface flows such as leakage, injectability, and fluid production. In this study, x-ray computed tomography scans of a fractured carbonate caprock were used to create three dimensional reconstructions of the fracture before and after reaction with CO{sub 2}-acidified brine (Ellis et al., 2011, Greenhouse Gases: Sci. Technol., 1:248-260). As expected, mechanical apertures were found to increase substantially, doubling and even tripling in some places. However, the surface geometry evolved in complex ways including ‘comb-tooth’ structures created from preferential dissolution of calcite in transverse sedimentary bands, and the creation of degraded zones, i.e. porous calcite-depleted areas on reacted fracture surfaces. These geometric alterations resulted in increased fracture roughness, as measured by surface Z{sub 2} parameters and fractal dimensions D{sub f}. Computational fluid dynamics (CFD) simulations were conducted to quantify the changes in hydraulic aperture, fracture transmissivity and permeability. The results show that the effective hydraulic apertures are smaller than the mechanical apertures, and the changes in hydraulic apertures are nonlinear. Overestimation of flow rate by a factor of two or more would be introduced if fracture hydrodynamic properties were based on mechanical apertures, or if hydraulic aperture is assumed to change proportionally with mechanical aperture. The differences can be attributed, in part, to the increase in roughness after reaction, and is likely affected by contiguous transverse sedimentary features. Hydraulic apertures estimated by the 1D statistical model and 2D local cubic law (LCL) model are consistently larger than those calculated from the CFD simulations. In addition, a novel ternary segmentation method was devised to handle the degraded zones, allowing for a bounding analysis of the effects on hydraulic properties. We found that the degraded zones account for less than 15% of the fracture volume, but cover 70% to 80% of the fracture surface. When the degraded zones are treated as part of the fracture, the fracture transmissivities are two to four times larger because the fracture surfaces after reaction are not as rough as they would be if one considers the degraded zone as part of the rock. Therefore, while degraded zones created during geochemical reactions may not significantly increase mechanical aperture, this type of feature cannot be ignored and should be treated with prudence when predicting fracture hydrodynamic properties.

roughness↗
DOE OSTI2022

Dynamical Study of Adsorbate-Induced Restructuring Kinetics in Bimetallic Catalysts Using the PdAu(111) Model System

The dynamic restructuring of bimetallic catalysts plays a crucial role in their catalytic activity and selectivity. In particular, catalyst pretreatment with species such as carbon monoxide and oxygen has been shown to be an effective strategy for tuning the surface composition and morphology. Mechanistic and kinetic understanding of such restructuring are fundamental to the chemistry and engineering of surface active sites but have remained challenging due to the large structural, chemical, and temporal degrees of freedom. Here, we combine time-resolved temperature-programmed infrared reflection absorption spectroscopy, ab initio thermodynamics, and machine-learning molecular dynamics to uncover previously unidentified timescale and kinetic parameters of in situ restructuring in Pd/Au(111), a highly relevant model system for dilute Pd-in-Au nanoparticle catalysts. The key innovation lies in utilizing CO not only as a chemically sensitive probe of surface Pd, but also as an agent that induces restructuring of the surface. Upon annealing in vacuum, as-deposited Pd islands became encapsulated by Au and partially dissolved into the subsurface, leaving behind isolated Pd monomers on the surface. Subsequent exposure to 0.1 mbar CO enabled Pd monomers to repopulate the surface up to 373 K, above which complete Pd dissolution occurred by 473 K, with apparent activation energies of 0.14 and 0.48 eV, respectively. Furthermore, these restructuring processes occurred over the span of ~1000 s at a given temperature. Such a minute-timescale dynamics not only elucidates the fluxional nature of alloy catalysts but also presents an opportunity to fine-tune the surface at moderate temperature and pressure conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Development of Wormholes in Laboratory-Scale Fractures: Perspectives From Three-Dimensional Simulations

Here, we investigate the development of wormholes in laboratory–scale fractures using three–dimensional numerical simulations. Well–controlled initial conditions, involving a small perturbation near the inlet of an otherwise flat fracture aperture field, were used to make a systematic study of the effects of flow rate and reaction rate on the aperture evolution. We find at least two characteristic wormhole shapes, which can be grouped within a phase diagram in the space of Péclet and Damköhler numbers. We investigate how this phase diagram depends on fracture geometry, specifically the length ( L ) and width ( W ) in comparison to the initial aperture ( h 0 ). This information is used to determine an effective Damköhler number that leads to a Péclet and length–independent phase boundary between wormholes and uniform dissolution. We relate these observations to experimental studies of wormhole formation in dissolving fractures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A high performance lithium–sulfur battery enabled by a fish-scale porous carbon/sulfur composite and symmetric fluorinated diethoxyethane electrolyte

A high performance lithium–sulfur (Li–S) battery comprising a symmetric fluorinated diethoxyethane electrolyte coupled with a fish-scale porous carbon/S composite electrode was demonstrated. 1,2-Bis(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was first studied as a new electrolyte solvent for Li–S chemistry. When co-mixed with 1,3-dioxolane (DOL), the DOL/TFEE electrolyte suppressed the polysulfide dissolution and shuttling reaction. Lastly, when coupled with a fish-scale porous carbon/S composite electrode, the Li–S cell exhibited a significantly high capacity retention of 99.5% per cycle for 100 cycles, which is far superior to the reported numerous systems.

1,2-bis(1,1,2,2-tetrafluoroethoxy) ethane↗
DOE OSTI2013

Effects of anode materials on resistive characteristics of NiO thin films

This letter shows that the NiO-based structure with different anodes has different resistive switching properties. A conical conductive filament (CF) model is proposed for oxygen vacancies distributed in NiO films. Modeling analysis reveals much larger dissolution velocity of CF near anodes than near cathodes during the reset process. Different interfaces shown in Auger electron spectroscopy can be bound with the model to reveal that CF is dissolved in the structure with Pt or Au as anodes, while CF remains constant if the anode material is Ti or Al, which can explain whether switching properties occur in the specific NiO-based structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

The use of amorphous boron powder enhances mechanical alloying in soft magnetic FeNbB alloy: A magnetic study

Saturation magnetization and magnetic anisotropy have been studied during mechanical alloying of Fe{sub 75}Nb{sub 10}B{sub 15} alloys prepared using crystalline and commercial amorphous boron. The evolution of saturation magnetization indicates a more efficient dissolution of boron into the matrix using amorphous boron, particularly for short milling times. The magnetization of the crystalline phase increases as boron is incorporated into this phase. Two milling time regimes can be used to describe the evolution of magnetic anisotropy: a first regime governed by microstrains and a second one mainly governed by crystal size and amorphous fraction.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Ultraviolet-driven white light generation from oxyfluoride glass co-doped with Tm{sup 3+}-Tb{sup 3+}-Eu{sup 3+}

Tm{sup 3+}-Tb{sup 3+}-Eu{sup 3+} co-doped oxyfluoride glasses, doped with about 3.0 mol. % TmF{sub 3}, 0.25 mol. % TbF{sub 3}, and 0.25 mol. % EuF{sub 3}, have been prepared by melt quenching technique. Under excitation at commercial 365 nm, the rare-earth co-dopants are all directly excited and emit in the blue, green, and red, respectively, without appreciable energy transfer amongst the co-dopants. Tint of the white luminescence can be adjusted by changing the ratio of the co-dopants. Properties of the glass host promote excellent dissolution of the co-dopants and low non-radiative decay rate. The white emission at 365 nm excitation is suitable for light emitting diodes applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Critical point analysis of phase envelope diagram

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile, dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Role of sonic energy on growth morphology and optical properties of ZnO:S nanostructures

ZnO nanopowders doped with sulphur were prepared by sonochemical method. The input power of ultrasound was varied as 40%, 50% and 60% of the maximum power (375 W) in both continuous and pulsed mode. XRD results show the average size of the nanoparticles is the least for those prepared with 50% input power as well as the micro-strain. FESEM studies showed the formation of nanorods clubbed together to form flower like structure for these samples. In rest of the cases, no definite morphology was obtained. High resolution transmission electron microscopy (HRTEM) reveals the formation of nanorods oriented along c-axis for those samples prepared with 50% input power. No cavitation at 40% and excessive dissolution at 60% may lead to this type of morphology. Absorption studies showed high absorbance for sulphur doped samples but this was highest for the samples prepared with 60% input power.

36 MATERIALS SCIENCE↗
DOE OSTI2014

In situ study on the effect of thermomigration on intermetallic compounds growth in liquid-solid interfacial reaction

Synchrotron radiation real-time imaging technology was carried out in situ to observe and characterize the effect of thermomigration on the growth behavior of interfacial intermetallic compounds (IMCs) in Cu/Sn/Cu solder joint during soldering. The thermomigration resulted in asymmetrical formation and growth of the interfacial IMCs. Cu{sub 6}Sn{sub 5} and Cu{sub 3}Sn IMCs formed at the cold end and grew rapidly during the whole soldering process. However, only Cu{sub 6}Sn{sub 5} IMC formed at the hot end and remained relatively thin until solidification. The IMCs at the cold end were nearly seven times thicker than that at the hot end after solidification. The Cu dissolution at the cold end was significantly restrained, while that at the hot end was promoted, which supplied Cu atoms to diffuse toward the cold end under thermomigration to feed the rapid IMC growth. Moreover, the thermomigration also caused asymmetrical morphology of the interfacial IMCs at the cooling stage, i.e., the Cu{sub 6}Sn{sub 5} IMC at the cold end transformed into facet structure, while that at the hot end remained scallop-type. The asymmetrical growth behavior of the interfacial IMCs was analyzed from the view point of kinetics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Fabrication of ultra-high aspect ratio silicon nanopores by electrochemical etching

We report on the formation of ultra-high aspect ratio nanopores in silicon bulk material using photo-assisted electrochemical etching. Here, n-type silicon is used as anode in contact with hydrofluoric acid. Based on the local dissolution of surface atoms in pre-defined etching pits, pore growth and pore diameter are, respectively, driven and controlled by the supply of minority charge carriers generated by backside illumination. Thus, arrays with sub-100 nm wide pores were fabricated. Similar to macropore etching, it was found that the pore diameter is proportional to the etching current, i.e., smaller etching currents result in smaller pore diameters. To find the limits under which nanopores with controllable diameter still can be obtained, etching was performed at very low current densities (several μA cm{sup −2}). By local etching, straight nanopores with aspect ratios above 1000 (∼19 μm deep and ∼15 nm pore tip diameter) were achieved. However, inherent to the formation of such narrow pores is a radius of curvature of a few nanometers at the pore tip, which favors electrical breakdown resulting in rough pore wall morphologies. Lowering the applied bias is adequate to reduce spiking pores but in most cases also causes etch stop. Our findings on bulk silicon provide a realistic chance towards sub-10 nm pore arrays on silicon membranes, which are of great interest for molecular filtering and possibly DNA sequencing.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Quantum chemical approach for condensed-phase thermochemistry: Proposal of a harmonic solvation model

We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor–liquid equilibration of water and ethanol, and dissolution of gaseous CO{sub 2} in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗