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At least 1,027 records · Page 57

Probing lithiation and delithiation of thick sintered lithium-ion battery electrodes with neutron imaging

As lithium-on (Li-ion) batteries increase in their prevalence and the range of applications expands, there is a need to understand and exploit the limits of electrochemical performance. Probing the internal processes in Li-ion batteries provides insights into the electrochemical characteristics of the cells as well as information necessary for rational cell design. In this manuscript an in situ method, neutron imaging, is applied to Li-ion full cells to track the lithiation/delithiation processes in the electrodes during discharge. The electrodes comprise thick sintered films of only active material, which improves the number of discrete points that are mapped for net changes in neutron intensity through the electrode. The lithiation/delithiation processes are qualitatively consistent with calculations of the Li + concentration and discharge profiles of the cells. These results illustrate that neutron imaging can experimentally probe and confirm limitations in the electrochemical performance of Li-ion full cells, particularly those with thick electrodes.

25 ENERGY STORAGE↗

Electrical resistivity tomography determines the spatial distribution of clay layer thickness and aquifer vulnerability, Kandal Province, Cambodia

Despite being rich in water resources, many areas of South East Asia face difficulties in securing clean water supply. This is particularly problematic in regions with a rapidly growing population. In this study, the spatial variability of the thickness of a clay layer, controlling surface – groundwater interactions that affect aquifer vulnerability, was investigated using electrical resistivity tomography (ERT). Data were acquired along two transects, showing significant differences in the imaged resistivities. Borehole samples were analyzed regarding particle density and composition, and linked to their resistivity. The obtained relationships were used to translate the field electrical resistivities into lithologies. Those revealed considerable variations in the thickness of the clay layer, ranging from 0 m up to 25 m. Geochemical data, highlighting zones of increased ingress of surface water into the groundwater, confirmed areas of discontinuities in the clay layer, which act as preferential flow paths. The results may guide urban planning of the Phnom Penh city expansion, in order to supply the growing population with safe water. The presented approach of using geophysics to estimate groundwater availability, accessibility, and vulnerability is not only applicable to Kandal Province, Cambodia, but also to many other areas of fast urbanization in South East Asia and beyond.

58 GEOSCIENCES↗

Through-thickness recrystallization characteristics of a laminated AA3xxx–AA6xxx aluminum alloy system

The through-thickness annealing behavior of a laminated AA3xxx–AA6xxx alloy system at 300 °C has been studied by scanning electron microscopy, electron backscatter diffraction analysis, electron probe micro-analysis, differential scanning calorimetry, and hardness measurement. Results show that the recrystallization process starts at the interface region between the AA3xxx (clad) and AA6xxx (core) layers. Subsequently, the recrystallization process front progresses into the core layer, while the clad layer is the last region to recrystallize. It is also found that precipitation precedes recrystallization in the entire laminate at the investigated temperature. The preferential onset of recrystallization at the interface region is attributed to the net driving pressure being the highest in this region. The factors that lead to such enhanced net driving pressure are (a) deformation incompatibility between the two alloy layers, (b) lower solute content of the interface, which also leads to lower volume fraction of precipitates, and (c) an accelerated rate of precipitate coarsening due to the presence of a higher density of dislocations. The gradual progress of recrystallization from the interface towards the core layer is dictated by precipitate coarsening and the dependence of its rate on the density of deformation-induced dislocations. The lower driving pressure due to lower work hardening capacity, high solute drag pressure due to Mn, and additional Zener drag from precipitates that form due to solute redistribution during annealing explain the late initiation of recrystallization in the clad layer. - Highlights: • The through-thickness recrystallization of a laminated system is investigated. • The early onset of recrystallization at the interface is discussed. • The effects of precipitation and coarsening on recrystallization are analyzed.

36 MATERIALS SCIENCE↗

Structural and electrical properties of Ce{sub 0.75}(Gd{sub 0.95−x}Sr{sub x}Ca{sub 0.05}){sub 0.25}O{sub 2−δ} thick film electrolyte

Graphical abstract: - Highlights: • Effects of Sr doping on electrical properties and structure were investigated. • The samples have higher conductivity and low activation energy. • Cause of increase oxygen vacancy concentration in the grain boundary. - Abstract: The effects of Sr doping on the electrical properties of Ce{sub 0.75}(Gd{sub 0.95−x}Sr{sub x}Ca{sub 0.05}){sub 0.25}O{sub 2−δ} (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05 mol%) electrolytes thick films were investigated. The samples sintered at 1400 °C for 8 h. X-ray diffraction (XRD) showed typical XRD patterns of a cubic fluorite structure, and the ionic conductivity was examined by AC impedance spectroscopy. From the experimental results, it was observed that Ce{sub 0.75}(Gd{sub 0.95−x}Sr{sub x}Ca{sub 0.05}){sub 0.25}O{sub 2−δ} (x = 0.04 mol%) electrolytes thick film have higher conductivity and minimum activation energy at 600 °C. This is explained in terms of the increased in the oxygen vacancy concentration at the grain boundary.

36 MATERIALS SCIENCE↗

Tin oxide thick film by doping rare earth for detecting traces of CO{sub 2}: Operating in oxygen-free atmosphere

Highlights: • La, Gd, and Lu doped SnO{sub 2} with their sensing properties toward CO{sub 2} were compared. • The microstructures of SnO{sub 2}-based nanoparticles were elaborately characterized. • La-SnO{sub 2} thick film shows superior response toward trace ppm CO{sub 2}. • Our sensing material can be recommended to employ in oxygen-free environment. - Abstract: SnO{sub 2} thick films doped with atomic ratios ranging from 0 up to 8 at.% La, 8 at.% Gd, 8 at.% Lu were fabricated, respectively, via hydrothermal and impregnation methods. The crystal phase, morphology, and chemical composition of the SnO{sub 2}-based nanoparticles were characterized by XRD, FE-SEM, EDX, HRTEM and XPS. Sensing properties of La-SnO{sub 2}, Gd-SnO{sub 2}, Lu-SnO{sub 2} films, as well as the pure SnO{sub 2} film, were analyzed toward CO{sub 2} in the absence of O{sub 2}. It was found that the optimal doping element was La and the best doping ratio was 4 at.%. The maximum response appeared at an operating temperature of 250 °C, on which condition the 4 at.% La-SnO{sub 2} exhibited a remarkable improvement of response from 5.12 to 29.8 when increasing CO{sub 2} concentration from 50 to 500 ppm. Furthermore, the working mechanism underlying such enhancement in CO{sub 2}-sensing functions by La additive in the absence of O{sub 2} was proposed and discussed.

36 MATERIALS SCIENCE↗

Nano-crystalline thin and nano-particulate thick TiO{sub 2} layer: Cost effective sequential deposition and study on dye sensitized solar cell characteristics

Highlights: • Thin TiO{sub 2} layer is deposited on conducting substrate using sol–gel based dip coating. • TiO{sub 2} nano-particles are synthesized using hydrothermal route. • Thick TiO{sub 2} particulate layer is deposited on prepared thin layer. • Dye sensitized solar cells are made using thin and thick layer based photo-anode. • Introduction of thin layer in particulate photo-anode improves the cell efficiency. - Abstract: A compact thin TiO{sub 2} passivation layer is introduced between the mesoporous TiO{sub 2} nano-particulate layer and the conducting glass substrate to prepare photo-anode for dye-sensitized solar cell (DSSC). In order to understand the effect of passivation layer, other two DSSCs are also developed separately using TiO{sub 2} nano-particulate and compact thin film based photo-anodes. Nano-particles are prepared using hydrothermal synthesis route and the compact passivation layer is prepared by simply dip coating the precursor sol prepared through wet chemical route. The TiO{sub 2} compact layer and the nano-particles are characterised in terms of their micro-structural features and phase formation behavior. It is found that introduction of a compact TiO{sub 2} layer in between the mesoporous TiO{sub 2} nano-particulate layer and the conducting substrate improves the solar to electric conversion efficiency of the fabricated cell. The dense thin passivation layer is supposed to enhance the photo-excited electron transfer and prevent the recombination of photo-excited electrons.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Reflectance dependence of polytetrafluoroethylene on thickness for xenon scintillation light

Many rare event searches including dark matter direct detection and neutrinoless double beta decay experiments take advantage of the high VUV reflective surfaces made from polytetrafluoroethylene (PTFE) reflector materials to achieve high light collection efficiency in their detectors. As the detectors have grown in size over the past decade, there has also been an increased need for ever thinner detector walls without significant loss in reflectance to reduce dead volumes around active noble liquids, outgassing, and potential backgrounds. We report on the experimental results to measure the dependence of the reflectance on thickness of two PTFE samples at wavelengths near 178 nm. No change in reflectance was observed as the wall thickness of a cylindrically shaped PTFE vessel immersed in liquid xenon was varied between 1 mm to 9.5 mm.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Comparison of gamma-ray spectral analysis methods for thick-walled UF 6 cylinders

Three data analysis methods were compared for gamma ray spectra collected by planar and coaxial high-purity germanium detectors (HPGe) on thick-walled uranium hexafluoride cylinders. The cylinder contents range from natural to low-enriched uranium (4.95% 235 U). Each spectrum was analyzed with the traditional 185.7 keV enrichment meter method, a 185.7/1001 keV ratio method, and the Fixed Energy Response Function Analysis with Multiple Efficiency (FRAM) software that utilizes low- and high-energy gamma rays and X-rays. When results for all cylinders were compared, the enrichment meter method and the 185.7/1001 keV peak ratio method consistently provided the most accurate data for all detector types. The error on the enrichment calculations analyzed with FRAM did not meet the international target value whereas those calculated with the enrichment meter and ratio method did. Enrichments calculated by FRAM were found to skew to higher values on natural uranium and to lower values on low-enriched uranium. FRAM calculated the least-precise enrichments; replicate analyses of single cylinders resulted in 235 U values that varied by as much as 19%. FRAM does have the significant advantages in that it does not require the use of calibration cylinders, infinite thickness criteria are not necessary, and it can be applied to any HPGe detector. Finally, if calibration cylinders are available, the enrichment meter and 185.7/1001 peak ratio are the recommended methods as they are the most accurate and precise.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

New method for level-lifetime measurements with thick scintillators

Level lifetimes provide key insight into the structure of atomic nuclei and serve as stringent tests of theoretical descriptions. Though several methods for determining level lifetimes exist for both reaction measurements and decay studies, here the focus is on techniques involving the direct measurement of time differences between population and subsequent depopulation of excited states. The techniques presented herein are broadly applicable across multiple timing ranges, but the approach is specifically described for the βγ timing method. A multi-step, amplitude-dependent time walk correction was employed to address the data analysis complications that arise from using thick scintillators for electron detection. Further, additional corrections for the depth of the interaction must also be performed when the parent isotope has been implanted into the detector. Techniques are presented for performing these time walk and depth of interaction corrections. Subsequently, a new Monte Carlo method utilizing measured detector responses obtained from the data, coupled with chi-square minimization, is presented for extracting excited state lifetimes ≳ 100 picoseconds. The framework of this Monte Carlo method is developed for the decay of a state in 68 Zn with a known 1.6 ps half life, which is considered prompt given the detection sensitivity of the technique, and then benchmarked using two other excited states in neutron-rich Ni isotopes with 120(34) ps and 1.05(3) ns half lives. Using this new method which takes into account the thick scintillator used, these same half lives were measured to be 135(10) ps and 1.04(24) ns, respectively. The overall good agreement demonstrates the validity of the technique.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Probing neutron-skin thickness with free spectator neutrons in ultracentral high-energy isobaric collisions

We show that the yield ratio of free spectator neutrons produced in high-energy 96 Zr+ 96 Zr to 96 Ru+ 96 Ru collisions is a clean probe of the neutron-skin thickness of colliding nuclei and the slope parameter L of the symmetry energy. The idea is demonstrated based on the proton and neutron density distributions via a state-of-the-art Skyrme-Hartree-Fock-Bogolyubov calculation. Among spectator nucleons given by the Glauber model, free spectator neutrons include those from direct production that survive from clusterization as well as those from deexcitation of heavy clusters described by the popular GEMINI model. More free neutrons are produced in collisions of 96 Zr nucleus due to its larger neutron skin, compared to those produced in collisions of 96 Ru nucleus with a smaller neutron skin. The difference of the free spectator neutron yield is further increased with the increasing difference of the neutron-skin thickness between 96 Zr and 96 Ru with a larger L value, and the increase in ultracentral collisions is particularly insensitive to model details and experimental uncertainties. Since the production of free spectator neutrons is not affected by the complicated dynamics in the mid-rapidity region, the ratio of their multiplicities in ultracentral isobaric collisions is a robust observable for constraining the neutron skin and L value.

79 ASTRONOMY AND ASTROPHYSICS↗

Measurement of nuclear interaction cross sections towards neutron-skin thickness determination

The accuracy of reaction theories used to extract properties of exotic nuclei from scattering experiments is often unknown or not quantified, but of utmost importance when, e.g., constraining the equation of state of asymmetric nuclear matter from observables as the neutron-skin thickness. In order to test the Glauber multiple-scattering model, the total interaction cross section of 12 C on carbon targets was measured at initial beam energies of 400, 550, 650, 800, and 1000 MeV/nucleon. The measurements were performed during the first experiment of the newly constructed R 3 B (Reaction with Relativistic Radioactive Beams) experiment after the start of FAIR Phase-0 at the GSI/FAIR facility with beam energies of 400, 550, 650, 800, and 1000 MeV/nucleon. The combination of the large-acceptance dipole magnet GLAD and a newly designed and highly efficient Time-of-Flight detector enabled a precise transmission measurement with several target thicknesses for each initial beam energy with an experimental uncertainty of ±0.4%. A comparison with the Glauber model revealed a discrepancy of around 3.1% at higher beam energies, which will serve as a crucial baseline for the model-dependent uncertainty in future fragmentation experiments.

Astronomy & Astrophysics↗

Effect of insulator end cap thickness on time-dependent Hartmann flow in a rotating mirror

We present a framework for analysing plasma flow in a rotating mirror. By making a series of physical assumptions, we reduce the magnetohydrodynamic (MHD) equations in a three-dimensional cylindrical system to a one-dimensional system in a shallow, cuboidal channel within a transverse magnetic field, similar to the Hartmann flow in ducts. We then solve the system both numerically and analytically for a range of values of the Hartmann number and calculate the dependence of the plasma flow speed on the thickness of the insulating end cap. We observe that the mean flow overshoots and decelerates before achieving a steady-state value, a phenomenon that the analytical model cannot capture. This overshoot is directly proportional to the thickness of the insulating end cap and the external electric field, with a weak dependence on the external magnetic field. Our simplified model can act as a benchmark for future simulations of the supersonic mirror device CMFX (centrifugal magnetic fusion experiment), which will employ more sophisticated physics and realistic magnetic field geometries.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Nanoparticle-Templated Thickness Controlled Growth, Thermal Stability, and Decomposition of Ultrathin Tin Sulfide Plates

Tin monosulfide (SnS) is a layered two-dimensional semiconductor attractive for instance for photovoltaics, optoelectronics, and valleytronics. However, these applications require synthesis of SnS flakes with controlled thickness and shape. Here we demonstrate the possibility of using Au nanoparticles to seed the nucleation, determine the position and control the thickness of the growing SnS plates. Further, we use in-situ transmission electron microscopy on individual ultrathin SnS flakes during annealing at high temperatures to establish their thermal stability and decomposition pathways, important due to the large surface areas of ultrathin flakes. We find that ultrathin SnS plates decompose rapidly at temperatures above 400 ºC. The decomposition invariably starts at the edges of the flakes and is highly anisotropic. Real-time observations show that while the {010} and the {110} facets are relatively stable and retract slowly, rapid removal of material along the < 100 > directions leads to the fast decay of {100} facets, which are thus replaced by extended {110} facets. The comparison of shapes developed during growth and sublimation establishes that the typical crystal habits observed for SnS and related group IV monochalcogenides are indeed kinetic growth shapes rather than equilibrium (Wulff) shapes determined by different facet surface free energies. Furthermore, these findings can further guide the design of growth experiments for achieving particular shapes of flakes of SnS and related layered crystals.

36 MATERIALS SCIENCE↗

Direct determination of solid-electrolyte interphase thickness and composition as a function of state of charge on a silicon anode

Using neutron reflectometry we have determined the thickness and chemistry of the solid-electrolyte interphase (SEI) layer grown on a silicon anode as a function of state of charge and during cycling. We show the chemistry of this SEI layer becomes more LiF like with increasing lithiation and more Li-C-O-F like with delithiation. More importantly the SEI layer thickness appears to increase (about 250 ) as the electrode becomes less lithiated and thins to 180 with increasing Li content (Li 3.7 Si). We attribute this breathing to the continual consumption of electrolyte with cycling.

25 ENERGY STORAGE↗

Ultralow Damping in Nanometer-Thick Epitaxial Spinel Ferrite Thin Films

Pure spin currents, unaccompanied by dissipative charge flow, are essential for realizing energy-efficient nanomagnetic information and communications devices. Thin-film magnetic insulators have been identified as promising materials for spin-current technology because they are thought to exhibit lower damping compared with their metallic counterparts. However, insulating behavior is not a sufficient requirement for low damping, as evidenced by the very limited options for low-damping insulators. Here, we demonstrate a new class of nanometer-thick ultralow-damping insulating thin films based on design criteria that minimize orbital angular momentum and structural disorder. Specifically, we show ultralow damping in <20 nm thick spinel-structure magnesium aluminum ferrite (MAFO), in which magnetization arises from Fe 3+ ions with zero orbital angular momentum. Here, these epitaxial MAFO thin films exhibit a Gilbert damping parameter of ~0.0015 and negligible inhomogeneous linewidth broadening, resulting in narrow half width at half-maximum linewidths of ~0.6 mT around 10 GHz. Our findings offer an attractive thin-film platform for enabling integrated insulating spintronics.

36 MATERIALS SCIENCE↗

Potential-Controlled Deposition of Multilayer CO 2 Reduction Catalyst Films onto Silicon Photoelectrodes Demonstrates Thickness-Dependent Catalytic Rates

Covalently attaching molecular catalysts to semiconductor surfaces yields promising hybrid photoelectrode architectures for reducing CO 2 to higher-value carbon products. Polymeric molecular catalyst films have higher loading densities than their monolayer counterparts, promising greater rates of solar fuel production. Using photoassisted diazonium electrografting, multilayered films of a Re(apbpy)(CO) 3 Cl CO 2 -reduction catalyst were attached to low-doped p-type Si (pSi). Parallel characterization of the newly formed films with ellipsometry, XPS, and ICP-MS revealed that catalyst loading increased with increasingly negative applied grafting potentials (Vgraft), providing us an experimental test bed to study the effects of film thickness on photocatalytic performance. Controlled-potential electrolysis experiments showed enhanced CO evolution rates on all photoelectrodes with increasingly negative applied potentials (V app ), with thicker films exhibiting the greatest rates of enhancement. Competitive proton reduction reactions at the Si surface were not strongly linked to V app but dependent on film thickness, with thicker films showing increased CO-to-H 2 production ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric and Long-term Aging Effects on the Electrical Properties of Variable Thickness WSe 2 Transistors

Atmospheric and long-term aging effects on electrical properties of WSe 2 transistors with various thicknesses are examined. While countless published studies report electrical properties of transition-metal dichalcogenide materials, many are not attentive to testing environment or to age of samples, which we have found significantly impacts results. Our as-fabricated exfoliated WSe 2 pristine devices are predominantly n-type, which is attributed to selenium vacancies. Transfer characteristics of as-fabricated devices measured in air then vacuum reveal physisorbed atmospheric molecules significantly reduced n-type conduction in air. First-principles calculations suggest this short-term reversible atmospheric effect can be attributed primarily to physisorbed H 2 O on pristine WSe 2 , which is easily removed from the pristine surface in vacuum due to the low adsorption energy. Devices aged in air for over 300 h demonstrate irreversibly increased p-type conduction and decreased n-type conduction. Moreover, they develop an extended time constant for recovery of the atmospheric adsorbents effect. Short-term atmospheric aging (up to approximately 900 h) is attributed to O 2 and H 2 O molecules physisorbed to selenium vacancies where electron transfer from the bulk and adsorbed binding energies are higher than the H 2 O-pristine WSe2. The residual/permanent aging component is attributed to electron trapping molecular O 2 and isoelectronic O chemisorption at selenium vacancies, which also passivates the near-conduction band gap state, p-doping the material, with very high binding energy. All effects reflected have the expected thickness dependence, namely, thinner devices are more sensitive to atmospheric and long-term aging effects.

36 MATERIALS SCIENCE↗

Control over Silica Particle Growth and Particle–Biomolecule Interactions Facilitates Silica Encapsulation of Mammalian Cells with Thickness Control

Over the past 20 years, many strategies utilizing sol–gel chemistry to integrate biological cells into silica-based materials have been reported. One such strategy, Sol-Generating Chemical Vapor into Liquid (SG-CViL) deposition, shows promise as an efficient encapsulation technique due to the ability to vary the silica encapsulation morphology obtained by this process through variation of SG-CViL reaction conditions. In this report, we develop SG-CViL as a tunable, multi-purpose silica encapsulation strategy by investigating the mechanisms governing both silica particle generation and subsequent interaction with phospholipid assemblies (liposomes and living cells). Using Dynamic Light Scattering (DLS) measurements, linear and exponential silica particle growth dynamics were observed which were dependent on deposition buffer ion constituents and ion concentration. Silica particle growth followed a cluster–cluster growth mechanism at acidic pH, and a monomer-cluster growth mechanism at neutral to basic pH. Increasing silica sol aging temperature resulted in higher rates of particle growth and larger particles. DLS measurements employing PEG-coated liposomes and cationic liposomes, serving as model phospholipid assemblies, revealed that electrostatic interactions promote more stable liposome–silica interactions than hydrogen bonding and facilitate silica coating on suspension cells. However, continued silica reactivity leads to aggregation of silica-coated suspension cells, revealing the need for cell isolation to tune deposited silica thickness. As a result, utilizing these mechanistic study insights, silica was deposited onto adherent HeLa cells under biocompatible conditions with micrometer-scale control over silica thickness, minimal cell manipulation steps, and retained cell viability over several days.

36 MATERIALS SCIENCE↗