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At least 721 records · Page 40

In Situ Chemical Imaging of Solid-Electrolyte Interphase Layer Evolution in Li–S Batteries

Parasitic reactions of electrolyte and polysulfide with the Li-anode in lithium sulfur (Li-S) batteries lead to the for-mation of solid electrolyte interphase (SEI) layers, which are the major reason behind severe capacity fading in these systems. Despite numerous studies, the evolution mechanism of the SEI layer and specific roles of polysulfides and oth-er electrolyte components are still unclear. We report an in-situ X-ray photoelectron spectroscopy (XPS) and chemical imaging analysis combined with ab initio molecular dynamics (AIMD) computational modeling to gain fundamental understanding regarding the evolution of SEI layers on Li-anodes within Li-S batteries. A multi-modal approach in-volving AIMD modeling and in-situ XPS characterization uniquely reveals the chemical identity and distribution of active participants in parasitic reactions as well as the SEI layer evolution mechanism. The SEI layer evolution has three major stages: the formation of a primary composite mixture phase involving stable lithium compounds (Li2S, LiF, Li2O etc); and formation of a secondary matrix type phase due to cross interaction between reaction products and elec-trolyte components, which is followed by a highly dynamic mono-anionic polysulfide (i.e. LiS5) fouling process. These new molecular-level insights into the SEI layer evolution on Li- anodes are crucial for delineating effective strategies for the development of Li–S batteries.

25 ENERGY STORAGE↗

Nanoscopic Imaging of Self-Propelled Ultrasmall Catalytic Nanomotors

Ultrasmall nanomotors (<100 nm) are highly desirable nanomachines for their size-specific advantages over their larger counterparts in applications spanning nanomedicine, directed assembly, active sensing, and environmental remediation. While there are extensive studies on motors larger than 100 nm, the design and understanding of ultrasmall nanomotors have been scant due to the lack of high-resolution imaging of their propelled motions with orientation and shape details resolved. Here, we report the imaging of the propelled motions of catalytically powered ultrasmall nanomotors─hundreds of them─at the nanometer resolution using liquid-phase transmission electron microscopy. These nanomotors are Pt nanoparticles of asymmetric shapes (“tadpoles” and “boomerangs”), which are colloidally synthesized and observed to be fueled by the catalyzed decomposition of NaBH4 in solution. Statistical analysis of the orientation and position trajectories of fueled and unfueled motors, coupled with finite element simulation, reveals that the shape asymmetry alone is sufficient to induce local chemical concentration gradient and self-diffusiophoresis to act against random Brownian motion. Our work elucidates the colloidal design and fundamental forces involved in the motions of ultrasmall nanomotors, which hold promise as active nanomachines to perform tasks in confined environments such as drug delivery and chemical sensing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct imaging of enhanced current collection on grain boundaries of Cu(In,Ga)Se{sub 2} solar cells

We report on direct imaging of current collection by performing conductive atomic force microscopy (C-AFM) measurement on a complete Cu(In,Ga)Se{sub 2} solar cell. The localized current was imaged by milling away the top conductive layer of the device by repeated C-AFM scans. The result exhibits enhanced photocurrent collection on grain boundaries (GBs) of CIGS films, consistent with the argument for electric-field-assisted carrier collection on the GBs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A fast microchannel plate-scintillator detector for velocity map imaging and imaging mass spectrometry

The time resolution achievable using standard position-sensitive ion detectors, consisting of a chevron pair of microchannel plates coupled to a phosphor screen, is primarily limited by the emission lifetime of the phosphor, around 70 ns for the most commonly used P47 phosphor. We demonstrate that poly-para-phenylene laser dyes may be employed extremely effectively as scintillators, exhibiting higher brightness and much shorter decay lifetimes than P47. We provide an extensive characterisation of the properties of such scintillators, with a particular emphasis on applications in velocity-map imaging and microscope-mode imaging mass spectrometry. The most promising of the new scintillators exhibits an electron-to-photon conversion efficiency double that of P47, with an emission lifetime an order of magnitude shorter. The new scintillator screens are vacuum stable and show no signs of signal degradation even over longer periods of operation.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Detection of melting by X-ray imaging at high pressure

The occurrence of partial melting at elevated pressure and temperature is documented in real time through measurement of volume strain induced by a fixed temperature change. Here we present the methodology for measuring volume strains to one part in 10{sup −4} for mm{sup 3} sized samples in situ as a function of time during a step in temperature. By calibrating the system for sample thermal expansion at temperatures lower than the solidus, the onset of melting can be detected when the melting volume increase is of comparable size to the thermal expansion induced volume change. We illustrate this technique with a peridotite sample at 1.5 GPa during partial melting. The Re capsule is imaged with a CCD camera at 20 frames/s. Temperature steps of 100 K induce volume strains that triple with melting. The analysis relies on image comparison for strain determination and the thermal inertia of the sample is clearly seen in the time history of the volume strain. Coupled with a thermodynamic model of the melting, we infer that we identify melting with 2 vol.% melting.

36 MATERIALS SCIENCE↗

Femtosecond time-resolved XUV + UV photoelectron imaging of pure helium nanodroplets

Liquid helium nanodroplets, consisting of on average 2 × 10{sup 6} atoms, are examined using femtosecond time-resolved photoelectron imaging. The droplets are excited by an extreme ultraviolet light pulse centered at 23.7 eV photon energy, leading to states within a band that is associated with the 1s3p and 1s4p Rydberg levels of free helium atoms. The initially excited states and subsequent relaxation dynamics are probed by photoionizing transient species with a 3.2 eV pulse and using velocity map imaging to measure time-dependent photoelectron kinetic energy distributions. Significant differences are seen compared to previous studies with a lower energy (1.6 eV) probe pulse. Three distinct time-dependent signals are analyzed by global fitting. A broad intense signal, centered at an electron kinetic energy (eKE) of 2.3 eV, grows in faster than the experimental time resolution and decays in ∼100 fs. This feature is attributed to the initially excited droplet state. A second broad transient feature, with eKE ranging from 0.5 to 4 eV, appears at a rate similar to the decay of the initially excited state and is attributed to rapid atomic reconfiguration resulting in Franck-Condon overlap with a broader range of cation geometries, possibly involving formation of a Rydberg-excited (He{sub n})* core within the droplet. An additional relaxation pathway leads to another short-lived feature with vertical binding energies ≳2.4 eV, which is identified as a transient population within the lower-lying 1s2p Rydberg band. Ionization at 3.2 eV shows an enhanced contribution from electronically excited droplet states compared to ejected Rydberg atoms, which dominate at 1.6 eV. This is possibly the result of increased photoelectron generation from the bulk of the droplet by the more energetic probe photons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma response measurements of non-axisymmetric magnetic perturbations on DIII-D via soft x-ray imaging

Recent observations on DIII-D have advanced the understanding of plasma response to applied resonant magnetic perturbations (RMPs) in both H-mode and L-mode plasmas. Three distinct 3D features localized in minor radius are imaged via filtered soft x-ray emission: (i) the formation of lobes extending from the unperturbed separatrix in the X-point region at the plasma boundary, (ii) helical kink-like perturbations in the steep-gradient region inside the separatrix, and (iii) amplified islands in the core of a low-rotation L-mode plasma. In this study, these measurements are used to test and to validate plasma response models, which are crucial for providing predictive capability of edge-localized mode control. In particular, vacuum and two-fluid resistive magnetohydrodynamic(MHD) responses are tested in the regions of these measurements. At the plasma boundary in H-mode discharges with n = 3 RMPs applied, measurements compare well to vacuum-field calculations that predict lobe structures. Yet in the steep-gradient region, measurements agree better with calculations from the linear resistive two-fluid MHD code, M3D-C1. Relative to the vacuum fields, the resistive two-fluid MHD calculations show a reduction in the pitch-resonant components of the normal magnetic field (screening), and amplification of non-resonant components associated with ideal kink modes. However, the calculations still over-predict the amplitude of the measuredperturbation by a factor of 4. In a slowly rotating L-mode plasma with n = 1 RMPs, core islands are observed amplified from vacuum predictions. Finally, these results indicate that while the vacuum approach describes measurements in the edge region well, it is important to include effects of extended MHD in the pedestal and deeper in the plasma core.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Velocity map imaging of O-atom products from UV photodissociation of the CH{sub 2}OO Criegee intermediate

UV excitation of jet-cooled CH{sub 2}OO X{sup 1}A′ to the excited B{sup 1}A′ electronic states results in dissociation to two spin-allowed product channels: H{sub 2}CO X{sup 1}A{sub 1} + O {sup 1}D and H{sub 2}CO a{sup 3}A″ + O {sup 3}P. In this study, the higher energy H{sub 2}CO a{sup 3}A″ + O {sup 3}P channel is characterized by velocity map imaging and UV action spectroscopy, in both cases utilizing 2 + 1 resonance enhanced multiphoton ionization detection of O {sup 3}P products, which complements a prior experimental study on the lower energy H{sub 2}CO X{sup 1}A{sub 1} + O {sup 1}D channel [Lehman et al., J. Chem. Phys. 139, 141103 (2013)]. Anisotropic angular distributions indicative of rapid dissociation are obtained at 330 and 350 nm, along with broad and unstructured total kinetic energy distributions that provide insight into the internal excitation of the H{sub 2}CO a{sup 3}A″ co-fragment. A harmonic normal mode analysis points to significant vibrational excitation of the CH{sub 2} wag and C–O stretch modes of the H{sub 2}CO a{sup 3}A″ fragment upon dissociation. At each UV wavelength, the termination of the kinetic energy distribution reveals the energetic threshold for the H{sub 2}CO a{sup 3}A″ + O {sup 3}P product channel of ca. 76 kcal mol{sup −1} (378 nm) and also establishes the dissociation energy from CH{sub 2}OO X{sup 1}A′ to H{sub 2}CO X{sup 1}A{sub 1} + O{sup 1}D products of D{sub 0} ≤ 49.0 ± 0.3 kcal mol{sup −1}, which is in accord with prior theoretical studies. The threshold for the H{sub 2}CO a{sup 3}A″ + O {sup 3}P channel is also evident as a more rapid falloff on the long wavelength side of the O {sup 3}P action spectrum as compared to the previously reported UV absorption spectrum for jet-cooled CH{sub 2}OO [Beames et al., J. Am. Chem. Soc. 134, 20045 (2012)]. Modeling suggests that the O {sup 3}P yield increases uniformly from 378 to 300 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Validation of full-wave simulations for mode conversion of waves in the ion cyclotron range of frequencies with phase contrast imaging in Alcator C-Mod

Mode conversion of fast waves in the ion cyclotron range of frequencies (ICRF) is known to result in current drive and flow drive under optimised conditions, which may be utilized to control plasma profiles and improve fusion plasma performance. To describe these processes accurately in a realistic toroidal geometry, numerical simulations are essential. Quantitative comparison of these simulations and the actual experimental measurements is important to validate their predictions and to evaluate their limitations. The phase contrast imaging (PCI) diagnostic has been used to directly detect the ICRF waves in the Alcator C-Mod tokamak. The measurements have been compared with full-wave simulations through a synthetic diagnostic technique. Recently, the frequency response of the PCI detector array on Alcator C-Mod was recalibrated, which greatly improved the comparison between the measurements and the simulations. In this study, mode converted waves for D-{sup 3}He and D-H plasmas with various ion species compositions were re-analyzed with the new calibration. For the minority heating cases, self-consistent electric fields and a minority ion distribution function were simulated by iterating a full-wave code and a Fokker-Planck code. The simulated mode converted wave intensity was in quite reasonable agreement with the measurements close to the antenna, but discrepancies remain for comparison at larger distances.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Imaging outside the box: Resolution enhancement in X-ray coherent diffraction imaging by extrapolation of diffraction patterns

Coherent diffraction imaging is a high-resolution imaging technique whose potential can be greatly enhanced by applying the extrapolation method presented here. We demonstrate the enhancement in resolution of a non-periodical object reconstructed from an experimental X-ray diffraction record which contains about 10% missing information, including the pixels in the center of the diffraction pattern. A diffraction pattern is extrapolated beyond the detector area and as a result, the object is reconstructed at an enhanced resolution and better agreement with experimental amplitudes is achieved. The optimal parameters for the iterative routine and the limits of the extrapolation procedure are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Comparison of implosion core metrics: A 10 ps dilation X-ray imager vs a 100 ps gated microchannel plate [Comparison of implosion core shape observations, 10 ps dilation X-ray imager vs 100 ps gated microchannel plate]

The dilation x-ray imager (DIXI) is a high-speed x-ray framing camera that uses the pulse-dilation technique to achieve a temporal resolution of less than 10 ps. This is a 10× improvement over conventional framing cameras currently employed on the National Ignition Facility (NIF) (100 ps resolution), and otherwise only achievable with 1D streaked imaging. A side effect of the dramatically reduced gate width is the comparatively lower detected signal level. Therefore we implement a Poisson noise reduction with non-local principal component analysis method to improve the robustness of the DIXI data analysis. Furthermore, we present results on ignition-relevant experiments at the NIF using DIXI. In particular we focus on establishing that/when DIXI gives reliable shape metrics (P 0 , P 2 and P 4 Legendre modes, and their temporal evolution/swings).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Sub-nanosecond single line-of-sight (SLOS) x-ray imagers (invited)

A new generation of fast-gated x-ray framing cameras have been developed that are capable of capturing multiple frames along a single line-of-sight with 30 ps temporal resolution. The instruments are constructed by integrating pulse-dilation electron imaging with burst mode hybrid-complimentary metal-oxide-semiconductor sensors. Two such instruments have been developed, characterized, and fielded at the National Ignition Facility and the OMEGA laser. These instruments are particularly suited for advanced x-ray imaging applications in Inertial Confinement Fusion and High energy density experiments. Here, we discuss the system architecture and the techniques required for tuning the instruments to achieve optimal performance. Characterization results are also presented along with planned future improvements to the design.

47 OTHER INSTRUMENTATION↗

HIGH-RESOLUTION LABORATORY SPECTRA OF THE λ193 CHANNEL OF THE ATMOSPHERIC IMAGING ASSEMBLY INSTRUMENT ON BOARD SOLAR DYNAMICS OBSERVATORY

Extreme ultraviolet spectra of C, O, F, Ne, S, Ar, Fe, and Ni have been excited in an electron beam ion trap and studied with much higher resolution than available on the Solar Dynamics Observatory (SDO) in order to ascertain the spectral composition of the SDO/Atmospheric Imaging Assembly (AIA) observations. We present our findings in the wavelength range 182-200 Å, which, overall, corroborate the working models of how to interpret the SDO/AIA data. We find, however, that the inclusion of a number of additional lines might improve the data interpretation.

74 ATOMIC AND MOLECULAR PHYSICS↗