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Wang, Chong M

Publications and source records attributed to Wang, Chong M.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Structure And Radiation Damage Behavior Of Epitaxial CrxMo1-x Alloy Thin Films On MgO

Phenomena related to the interaction of point defects and dopants with grain boundaries and interfaces have been very well documented. However, a quantitative understanding of such an interaction is still missing. In this paper we explore the correlation between radiation damage and interface structure. In doing so, CrxMo1-x(001) films of thickness ~100 nm were epitaxially grown on MgO (001) using molecular beam epitaxy. The interface dislocation density can be systematically varied by controlling the composition of the film. This system allows us to probe the response of the defects generated during the irradiation to the interface dislocation density. The microstructural features of these films before and after irradiation are carefully studied using high resolution scanning/transmission electron microscopy and electron diffraction. It has been found that the film/substrate system is very resistant to ion-induced irradiation damage. No visible point defect clusters, dislocation network or amorphization has been identified, which is contrasted with other materials of either metallic or ionic bonding. We conclude that the defects in the present system appear to be either sub-microscopic and highly dispersed or are annihilated during the irradiation process. Further detailed work is needed to identify the spatial distribution of the defects.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Studying The Kinetics Of Crystalline Silicon Nanoparticle Lithiation With In-Situ Transmission Electron Microscopy

Silicon is an attractive high-capacity anode material for Li-ion batteries, but a comprehensive understanding of the massive ~300% volume change and fracture during lithiation/delithiation is necessary to reliably employ Si anodes. Here, in-situ transmission electron microscopy (TEM) of the lithiation of crystalline Si nanoparticles reveals that the reaction slows down as it progresses into the particle interior. Analysis suggests that this behavior is due to the influence of mechanical stress at the reaction front on the driving force for the reaction. These experiments give insight into the factors controlling the kinetics of this unique reaction.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Carbon dioxide-assisted fabrication of highly uniform submicron-sized colloidal carbon spheres via hydrothermal carbonization using soft drink

An eco-friendly and economical method for the formation of uniform-sized carbon spheres by hydrothermal dehydration/condensation of a commercial carbonated beverage at 200 oC is reported. CO2 dissolved in the beverage accelerates the dehydration kinetics of the dissolved sugar molecules leading to production of homogeneous carbon spheres having a diameter less than 850 nm. In the presence of CO2, the rough surface of these carbon spheres likely results from continuous Ostwald ripening of constituent microscopic carbon-containing spheres that are formed by subsequent polymerization of intermediate HMF molecules.

beverage↗
DOE OSTI2012

Conflicting Roles Of Nickel In Controlling Cathode Performance In Lithium-ion Batteries

A variety of approaches are being made to enhance the performance of lithium ion batteries. Incorporating multi-valence transition metal ions into metal oxide cathodes has been identified as an essential approach to achieve the necessary high voltage and high capacity. However, the fundamental mechanism that limits their power rate and cycling stability remains unclear. The power rate strongly depends on the lithium ion drift speed in the cathode. Crystallographically, these transition metal-based cathodes frequently have a layered structure. In the classic wisdom, it is accepted that lithium ion travels swiftly within the layers moving out/in of the cathode during the charge/discharge. Here, we report the unexpected discovery of a thermodynamically driven, yet kinetically controlled, surface modification in the widely explored lithium nickel manganese oxide cathode material, which may inhibit the battery charge/discharge rate. We found that during cathode synthesis and processing before electrochemical cycling in the cell nickel can preferentially move along the fast diffusion channels and selectively segregate at the surface facets terminated with a mix of anions and cations. This segregation essentially blocks the otherwise fast out/in pathways for lithium ions during the charge/discharge. Therefore, it appears that the transition metal dopant may help to provide high capacity and/or high voltage, but can be located in a “wrong” location that blocks or slows lithium diffusion, limiting battery performance. In this circumstance, limitations in the properties of Li-ion batteries using these cathode materials can be determined more by the materials synthesis issues than by the operation within the battery itself.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Pertechnetate (TcO4-) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA

Technetium is an important environmental contaminant introduced by the processing and disposal of irradiated nuclear fuel and atmospheric nuclear tests. Under oxic conditions technetium is soluble and exists as pertechnatate anion (TcO4-), while under anoxic conditions Tc is usually insoluble and exists as precipitated Tc(IV). Here we investigated abiotic Tc(VII) reduction in mineralogically heterogeneous, Fe(II)-containing sediments. The sediments were collected from a 55 m borehole that sampled a semi-confined aquifer at the Hanford Site, USA that contained a dramatic redox transition zone. One oxic facies (18.0-18.3 m) and five anoxic facies (18.3-18.6 m, 30.8-31.1 m, 39.0-39.3 m, 47.2-47.5 m and 51.5-51.8 m) were selected for this study. Chemical extractions, X-ray diffraction, electron microscopy, and Mössbauer spectroscopy were applied to characterize the Fe(II) mineral suite that included: Fe(II)-phyllosilicates, pyrite, magnetite and siderite. The Fe(II) mineral phase distribution differed between the sediments. Sediment suspensions were adjusted to the same 0.5 M HCl extracted Fe(II) concentration (0.6 mM) for Tc(VII) reduction experiments. Aqueous Fe was low in all sediment suspensions (<2 μM) and below the Fe(II)aq detection limit (10 μM). Technetium(VII) reduction occurred in all anoxic sediments at depths greater than 18.3 m and reaction time differed significantly between the sediments (8-219 d). Mössbauer analysis of the Tc-reacted, 30.8-31.1 m sediment confirmed that Tc(VII) was reduced by solid-phase Fe(II), with siderite and Fe(II)-containing phyllosilicates implicated as redox reactive phases. Technetium-XAS analysis demonstrated that Tc associated with sediments was in the Tc(IV) valence state and immobilized as clusters of a TcO2·nH2O-like phase. The speciation of redox product Tc(IV) was not affected by reduction rate or Fe(II) mineralogy.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2012

Pb nanowire formation on Al/lead zirconate titanate surfaces in high-pressure hydrogen

Thin films of Al on lead zirconate titanate (PZT) annealed in high-pressure hydrogen at 100C exhibit surface Pb nanowire growth. Wire diameter is approximately 80 nm and length can exceed 100 microns. Based on microstructural analysis using electron microscopy and ion scattering, a vapor-solid scheme with hydrogen as a carrier gas was proposed as a growth mechanism. We expect that these observations may lead to controlled Pb nanowires growth through pattering of the Al film.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Hollow Core-Shell Structured Porous Si-C Nanocomposites for Li-Ion Battery Anodes

Hollow core-shell structured porous Si-C nanocomposites with void space up to tens of nanometers are designed to accommodate the volume expansion during lithiation for high-performance Li-ion battery anodes. An initial capacity of {approx}760 mAh/g after formation cycles (based on the entire electrode weight) with {approx}86% capacity retention over 100 cycles is achieved at a current density of 1 A/g. Good rate performance is also demonstrated.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Highly Dispersed and Active ReOx on Alumina-Modified SBA-15 Silica for 2-Butanol Dehydration

SBA-15 silica supported rhenium catalysts were synthesized using solution-based atomic layer deposition method, and their activity and stability were studied in the acid-catalyzed 2-butanol dehydration. We find that ReOx/SBA-15 exhibited an extremely high initial activity but a fast deactivation for 2-butanol dehydration at 90-105 C. Fast deactivation was likely due to the sintering, sublimation, and reduction of rhenia as confirmed by TEM, elemental analysis, and in situ UV vis (DRS) measurements. To overcome these issues, ReOx/AlOx/SBA-15 catalysts with significantly improved stability were prepared by first modifying the surface identity of SBA-15 with alumina followed by dispersion of rhenia using atomic layer deposition. The AlOx phase stabilizes the dispersion of small and uniform rhenia clusters (<2 nm) as as confirmed by TEM, STEM and UV-vis (DRS) characterizations. Additional 27Al MAS NMR characterization revealed that modification of the SBA-15 surface with alumina introduces a strong interaction between rhenia and alumina, which consequently improves the stability of supported rhenia catalysts by suppressing the sintering, sublimation, and reduction of rhenia albeit at a moderately reduced initial catalytic dehydration activity

2-butanol dehydration↗
DOE OSTI2012

Three-dimensional Chemical Imaging of Embedded Nanoparticles using Atom Probe Tomography

Analysis of nanoparticles is often challenging especially when they are embedded in a matrix. Hence, we have used laser-assisted atom probe tomography (APT) to analyze the Au-nanoclusters synthesized in situ using ion beam implantation in single crystal MgO matrix. APT analysis along with scanning transmission electron microscopy and energy dispersive spectroscopy (STEM-EDS) indicated that the nanoparticles have an average size ~ 8 - 12 nm. While it is difficult to analyze the composition of individual nanoparticles using STEM, APT analysis can give three dimensional compositions of the same. It was shown that the maximum Au-concentration in the nanoparticles increases with increasing particle size, with a maximum Au-concentration of up to 50%.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2012

The Effect of Metallic Coatings and Crystallinity on the Volume Expansion of Silicon during Electrochemical Lithiation and Delithiation

Applying surface coatings to alloying anodes for Li-ion batteries can improve rate capability and cycle life, but it is unclear how this second phase affects mechanical deformation during electrochemical reaction. Here, in-situ transmission electron microscopy is employed to investigate the electrochemical lithiation and delithiation of silicon nanowires (NWs) with copper coatings. When copper is coated on one sidewall, the NW bilayer structure bends due to length changes in the silicon during delithiation. Tensile hoop stress causes conformal copper coatings to fracture during lithiation without undergoing bending deformation. In addition, in-situ and ex-situ observations indicate that a copper coating plays a role in suppressing volume expansion during lithiation. Finally, the deformation characteristics and dimensional changes of amorphous, polycrystalline, and single-crystalline silicon are compared and related to observed electrochemical behavior. This study reveals important aspects of the deformation process of silicon anodes, and the results suggest that metallic coatings can be used to improve rate behavior and to manage or direct volume expansion in optimized silicon anode frameworks.

Energy↗
DOE OSTI2012

In Situ TEM Investigation of Congruent Phase Transition and Structural Evolution of Nanostructured Silicon/Carbon Anode for Lithium Ion Batteries

It is well known that upon lithiation both crystalline and amorphous Si transform to a armorphous LixSi phase, which subsequently crystallizes to a (Li, Si) crystalline compound, either Li15Si or Li22Si5. Up to date, the detailed atomistic mechanism of this phase transformation, and degradation process in nanostructured Si, are not fully understood. Here, we report the microstructural evolution and phase transformation characteristic of a specially designed amorphous silicon (a-Si) coated carbon nanofiber (CNF) composite during charge/discharge process using in-situ TEM and density function theory molecular dynamic (DFT-MD) calculation. We found that the crystallization of Li15Si4 from amorphous LixSi is a spontaneous, congruent phase transition process without phase separation or large scale atomic motion, which is drastically different from what is expected from a classic nucleation and growth process. The a-Si layer is strongly bonded to the CNF and no spallation or cracking is observed during the early stages of cyclic charge/discharge. Reversible volume expansion/contraction upon charge/discharge is fully accommodated along the radial direction. However, with progressive cycling, damage in the form of surface roughness was gradually accumulated on the coating layer, which is believed to be the mechanism for the eventual capacity fade of the composite anode during long term charge/discharge cycling.

25 ENERGY STORAGE↗
DOE OSTI2012

Factors Affecting the Battery Performance of Anthraquinone-based Organic Cathode Materials

Two organic cathode materials based on poly(anthraquinonyl sulfide) structure with different substitution positions were synthesized and their electrochemical behavior and battery performances were investigated. The substitution positions on the anthraquinone structure, binders for electrode preparation and electrolyte formulations have been found to have significant effects on the battery performances of such organic cathode materials. The substitution position with less steric stress has higher capacity, longer cycle life and better high-rate capability. Polyvinylidene fluoride binder and ether-based electrolytes are favorable for the high capacity and long cycle life of the quinonyl organic cathodes.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Structural characterization of epitaxial CrxMo1-x alloy thin films

To develop a model system containing regularly-spaced misfit dislocations for studies of the radiation resistance of nanoscale defects, epitaxial thin films of Cr, Mo, and Cr{sub x}Mo{sub 1-x} alloys were deposited on MgO(001) by molecular beam epitaxy. Film compositions were chosen to vary the lattice mismatch with MgO. The film structure was investigated with x-ray diffraction (XRD), Rutherford backscattering spectrometry (RBS), and scanning transmission electron microscopy (STEM). Epitaxial films with reasonably high crystalline quality and abrupt interfaces were achieved at a relatively low deposition temperature, as confirmed by STEM. However, it was found by XRD and RBS in the channeling geometry that increasing the Mo content of the CrMo alloy films degraded the crystalline quality, despite the improved lattice match with MgO. XRD rocking curve data indicated that regions of different crystalline order may be present within the films with higher Mo content. This is tentatively ascribed to spinodal decomposition into Cr-rich and Mo-rich regions, as predicted by the Cr{sub x}Mo{sub 1-x} phase diagram.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Monodisperse Au11 Clusters Prepared by Soft Landing of Mass Selected Ions

Preparation of clean monodisperse samples of clusters and nanoparticles for characterization using cutting-edge analytical techniques is essential to understanding their size-dependent properties. Herein, we report a general method for the preparation of high surface coverage samples of monodisperse clusters containing an exact number of atoms. Polydisperse solutions of diphosphine-capped gold clusters were produced by reduction synthesis. Electrospray ionization was used to introduce the clusters into the gas phase where they were filtered by mass-tocharge ratio allowing clusters of a selected size to be deposited onto carbon coated copper grids at well controlled kinetic energies. Scanning transmission electron microscopy (STEM) analysis of the soft landed clusters confirms their monodispersity and high coverage on the substrate. The soft landing approach may be extended to other materials compatible with an array of available ionization techniques and, therefore, has widespread utility as a means for controlled preparation of monodisperse samples of nanoparticles and clusters for analysis by transmission electron microscopy (TEM)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

The Mineralogic Transformation of Ferrihydrite Induced by Heterogeneous Reaction with Bioreduced Anthraquinone Disulfonate (AQDS) and the Role of Phosphate

Anthraquinone-2-6-disulfonate (AQDS) enhances electron donor utilization and mineral product crystallization in studies of Fe(III) oxide reductive mineralization by metal reducing bacteria (MRB) through heterogeneous redox reaction. In spite of the strong effect of AQDS in these systems, little information exits on its direct role in reductive mineralization. To provide such insights, bioreduced AQDS (AH2DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH2DS oxidation coupled with Fe(III) reduction occurred within 0.13-1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. P inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)]=0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)aq system, while AQDS was more effective than Fe(II)aq in promoting magnetite formation. The direct AH2DS-driven reductive reaction pathway produced mineral products that were different from AH2DS-ferrihydite-MRB systems, particularly in presence of P.

58 GEOSCIENCES↗
DOE OSTI2011

Effect of reductive treatments on Pt behavior and NOx storage in lean NOx trap catalysts

Lean NOx trap (LNT) catalysts represent a promising approach to meet increasingly stringent NOx emission regulations on diesel and other lean-burn engines. Pt material properties, including dispersion and particle size, are known to be important factors in determining NOx uptake performance, since Pt provides active sites for NO oxidation to NO2 necessary for storing NOx as nitrates, and for the reduction of nitrates to N2. In this work, the physicochemical properties of Pt in Pt-BaO/Al2O3 LNT catalysts, such as the Pt accessible surface area and particle size, were investigated by using various tools, such as irreversible volumetric H2 chemisorption, high resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD), following successive reductive treatments at elevated temperatures. NOx uptake activities were also measured to establish a relationship between the properties of Pt and NOx storage following identical high-temperature reductive treatments. We find that the reductive treatments of Pt-BaO/Al2O3 lean NOx trap catalysts at temperatures up to 500 ºC promote a significant increase in NOx uptake explained, in part, by an induced close interaction between Pt and BaO phases in the catalyst, thus enabling facilitation of the NOx storage process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Microstructure of the Native Oxide Layer on Ni and Cr-doped Ni Nanoparticles

Metallic or alloy nanoparticles exposed to air at room temperature will be instantaneously oxidized and covered by an oxide layer. However, for most cases, the true structural nature of the oxide layer formed at this stage is hard to determine. In this paper, we report the structure, morphology, and electronic structure (the density of state of both valence and conduction bands measured by a combination of XPS and EELS) of pure Ni and Cr-doped Ni nanoparticles synthesized using a cluster deposition process. Structural characterization carried out at the atomic level using aberration corrected high resolution transmission electron microscopy (HRTEM) in combination with electron and x-ray diffractions reveals that both pure Ni and Cr-doped Ni particles exposed to air at room temperature similarly possesses a core-shell structure of metal core covered by an oxide layer of typically 1.6 nm in thickness. There exists a critical size of ~ 6 nm, below which the particle is fully oxidized. The oxide particle corresponds to the rock-salt structured NiO and is faceted on the (001) planes. XPS of O-1s shows a strong peak that is attributed to (OH)-, which in combination with the atomic level HRTEM imaging indicates that the very top layer of the oxide is hydrolyzed as Ni(OH)2. Chemical composition analysis using EDS, EELS, and XPS indicates that the Cr dopant at the level of ~ 5at% forms solid solution with the Ni lattice. The Cr shows no segregation on the surface or preferential oxidation during the initial oxidation.

77 NANOSCIENCE AND NANOTECHNOLOGY↗