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At least 271 records · Page 15

Li-rich cathodes for rechargeable Li-based batteries: reaction mechanisms and advanced characterization techniques

Due to their high specific capacities beyond 250 mA h g -1 , lithium-rich oxides have been considered as promising cathodes for the next generation power batteries, bridging the capacity gap between traditional layered-oxide based lithium-ion batteries and future lithium metal batteries such as lithium sulfur and lithium air batteries. However, the practical application of Li-rich oxides has been hindered by formidable challenges. To address these challenges, the understanding of their electrochemical behaviors becomes critical and is expected to offer effective guidance for both materials and cell development. This work aims to provide fundamental insights into the reaction mechanisms, electrochemical challenges and modification strategies of lithium-rich oxides. We first summarize the research history, the pristine structures, and the classification of lithium-rich oxides. Then we review the critical reaction mechanisms that are closely related to their electrochemical features and performances, such as lattice oxygen oxidation, oxygen vacancy formation, transition-metal migration, layered to spinel transitions, ‘two-phase mechanism’, and lattice evolution. These discussions are coupled with state-of-the-art characterization techniques. As a comparison, the anionic redox reactions of layered sodium transition metal oxides are also discussed. Finally, after a brief overview of the correlation among the aforementioned mechanisms, we provide perspectives on the rational design of lithium-rich oxides with high energy densities and long-term cycling stability.

25 ENERGY STORAGE↗

Oxygen redox activities governing high-voltage charging reversibility of Ni-rich layered cathodes

A schematic illustration indicative of the improved structural reversibility through stabilizing oxidized oxygen by Al doping. The chemical reactions and phase transitions at high voltages are generally considered to determine the electrochemical properties of high-voltage layered cathodes such as Ni-rich rhombohedral oxides. Even if significantly higher SOCs (states-of-charge) are utilized above the capability of transition metal redox (primarily Ni and Co), the effect of oxygen redox on Ni-rich rhombohedral oxides still looks mysterious thereby necessitating research that can clarify the relationship between redox reactions and phase transitions. Here, we performed a comprehensive and comparative study of the cationic and anionic redox reactions, as well as the structural evolution of a series of commercial Ni-rich layered oxides with and without Al doping. We combined the results from X-ray spectroscopy, operando electrochemical mass spectrometry, and neutron diffraction with electrochemical properties and thereby revealed the different oxygen redox activities associated with structural and electrochemical degradations. We reveal that Al doping suppresses the irreversible oxygen release but enhances the lattice oxygen oxidization. With this modulated oxygen redox activity, the Ni-rich layered oxides’ notorious H2–H3 structural phase transition becomes highly reversible. Our findings disentangle the different oxygen redox activities during high-voltage cycling and clarify the role of dopants in the Ni-rich layered oxides in terms of structural and electrochemical stability, shedding light on the future direction of optimizing layered cathode materials for safer high energy-density secondary batteries.

Lee, Gi-Hyeok↗

Vacancy enhanced formation and phase transition of Cu-rich precipitates in α - iron under neutron irradiation

In this paper, we employed both molecular statics and molecular dynamics simulation methods to investigate the role of vacancies in the formation and phase transition of Cu-rich precipitates in α-iron. The results indicated that vacancies promoted the diffusion of Cu atoms to form Cu-rich precipitates. After Cu-rich precipitates formed, they further trapped vacancies. The supersaturated vacancy concentration in the Cu-rich precipitate induced a shear strain, which triggered the phase transition from bcc to fcc structure by transforming the initial bcc (110) plane into fcc (111) plane. In addition, the formation of the fcc-twin structure and the stacking fault structure in the Cu-rich precipitates was observed in dynamics simulations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

ON INFRARED EXCESSES ASSOCIATED WITH Li-RICH K GIANTS

Infrared (IR) excesses around K-type red giants (RGs) have previously been discovered using Infrared Astronomy Satellite (IRAS) data, and past studies have suggested a link between RGs with overabundant Li and IR excesses, implying the ejection of circumstellar shells or disks. We revisit the question of IR excesses around RGs using higher spatial resolution IR data, primarily from the Wide-field Infrared Survey Explorer. Our goal was to elucidate the link between three unusual RG properties: fast rotation, enriched Li, and IR excess. Our sample of RGs includes those with previous IR detections, a sample with well-defined rotation and Li abundance measurements with no previous IR measurements, and a large sample of RGs asserted to be Li-rich in the literature; we have 316 targets thought to be K giants, about 40% of which we take to be Li-rich. In 24 cases with previous detections of IR excess at low spatial resolution, we believe that source confusion is playing a role, in that either (a) the source that is bright in the optical is not responsible for the IR flux, or (b) there is more than one source responsible for the IR flux as measured in IRAS. We looked for IR excesses in the remaining sources, identifying 28 that have significant IR excesses by ∼20 μm (with possible excesses for 2 additional sources). There appears to be an intriguing correlation in that the largest IR excesses are all in Li-rich K giants, though very few Li-rich K giants have IR excesses (large or small). These largest IR excesses also tend to be found in the fastest rotators. There is no correlation of IR excess with the carbon isotopic ratio, {sup 12}C/{sup 13}C. IR excesses by 20 μm, though relatively rare, are at least twice as common among our sample of Li-rich K giants. If dust shell production is a common by-product of Li enrichment mechanisms, these observations suggest that the IR excess stage is very short-lived, which is supported by theoretical calculations. Conversely, the Li-enrichment mechanism may only occasionally produce dust, and an additional parameter (e.g., rotation) may control whether or not a shell is ejected.

79 ASTRONOMY AND ASTROPHYSICS↗

Theoretical study of triaxial shapes of neutron-rich Mo and Ru nuclei

Here, whether atomic nuclei can possess triaxial shapes at their ground states is still a subject of ongoing debate. According to theory, good prospects for low-spin triaxiality are in the neutron-rich Mo-Ru region. Recently, transition quadrupole moments in rotational bands of even-mass neutron-rich isotopes of molybdenum and ruthenium nuclei have been measured. The new data have provided a challenge for theoretical descriptions invoking stable triaxial deformations. The purpose of this study is to understand experimental data on rotational bands in the neutron-rich Mo-Ru region, we carried out theoretical analysis of moments of inertia, shapes, and transition quadrupole moments of neutron-rich even-even nuclei around 110 Ru using self-consistent mean-field and shell model techniques. Methods: To describe yrast structures in Mo and Ru isotopes, we use nuclear density functional theory (DFT) with the optimized energy density functional UNEDF0. We also apply triaxial projected shell model (TPSM) to describe yrast and positive-parity, near-yrast band structures. As a result, our self-consistent DFT calculations predict triaxial ground-state deformations in 106,108 Mo and 108,110,112 Ru and reproduce the observed low-frequency behavior of moments of inertia. As the rotational frequency increases, a negative-gamma structure, associated with the aligned ν(h 11/2 ) 2 pair, becomes energetically favored. The computed transition quadrupole moments vary with angular momentum, which reflects deformation changes with rotation; those variations are consistent with experiment. The TPSM calculations explain the observed band structures assuming stable triaxial shapes. Lastly, the structure of neutron-rich even-even nuclei around Ru-110 is consistent with triaxial shape deformations. Our DFT and TPSM frameworks provide a consistent and complementary description of experimental data.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Shape evolution in neutron-rich odd-even 105–109 Nb isotopes

Background: Neutron-rich nuclei around 𝑍 ≈ 40 are well known for exhibiting multiple shape transitions. Here, this region shows one of the sharpest shape transitions in the nuclear chart, evolving from a spherical vibrator at 𝑁 = 58 to a strongly deformed prolate shape at 𝑁 = 60. The largest deformations are observed for 38 Sr and 40 Zr . This abrupt shape transition disappears at 𝑍 = 36 and below, where a shape transition from spherical to oblate nuclei is predicted. On the other hand, for 𝑍 ≥ 42 and 𝑁 ≥ 60, the shape is known to evolve from axial to triaxial. While the even-𝑍 nuclei in this region have already been extensively studied, new insights can be gained from the studies of odd-𝑍 isotopes for a better understanding of the underlying mechanisms driving these phenomena. Purpose: The 41 Nb nuclei lie at the boundary between axially deformed Zr and triaxially deformed Mo nuclei. This work investigates the nuclear structure of very neutron-rich Nb nuclei up to 𝑁 = 68. The goal is to understand how the nuclear shape evolves as a function of isospin in this isotopic chain and provide new insights into the emergence of triaxial deformation. Methods: The structure of the neutron-rich Nb isotopes was investigated using state-of-the-art high-resolution 𝛾-ray spectroscopy of fission fragments produced via two different fission reactions. The use of 9 Be ⁢( 238 U, 𝑓) inverse kinematics, with a detection system comprising AGATA, EXOGAM, and VAMOS++, enabled the measurement of prompt and delayed 𝛾 rays from isotopically identified fission fragments, and 𝛾−𝛾−𝛾−𝛾 highfold data were obtained from a spontaneous fission source of 252 Cf using the Gammasphere array. Results: The level scheme of 105 Nb has been significantly extended, with the addition of two negative-parity bands observed for the first time. A new level scheme is proposed for 107 Nb, which is not in agreement with an earlier measurement, and new levels and transitions have been added to the very neutron-rich 109 Nb. The degree of triaxiality of the new bands is discussed on the basis of signature splitting analysis. The recently reported level scheme of 99 Nb has been revised. Conclusions: This systematic study on the Nb isotopic chain, compared to Zr and Mo, indicates that while the ground-state band exhibits a triaxial deformation, attributed to a proton hole coupled to a triaxially deformed Mo core, the negative-parity bands, based on isomeric bandheads, display an axially symmetric deformed structure, similar to that observed in the Zr isotopes, revealing the existence of a shape coexistence in the neutron-rich Nb nuclei.

Abushawish, M. [Université Claude-Bernard Lyon 1 (↗

Managing Rich Metadata in High-Performance Computing Systems Using a Graph Model

High-performance computing (HPC) systems generate huge amounts of metadata about different entities such as jobs, users, and files. Existing systems can efficiently record and manage part of these metadata, mainly the POSIX metadata of data files (e.g., file size, name, and permissions mode). But another important set of metadata, referred to as "rich" metadata in this study, which record not only wider range of entities (e.g., running processes and jobs) but also more complex relationships between them, are mostly missing in current HPC systems. Yet such rich metadata are critical for supporting many advanced data management functions such as identifying data sources and parameters behind a given result; auditing data usage; or understanding details about how inputs are transformed into outputs. To uniformly and efficiently manage the rich metadata generated in HPC systems, We propose to utilize a graph model in this study. We identify the key challenges of implementing such a graph-based HPC rich metadata management system and present GraphMeta, a graph-based rich metadata management system designed and optimized for HPC platforms, to tackle these challenges. In conclusion, extensive evaluations on both synthetic and real HPC metadata workloads show its advantages in both performance and scalability compared with existing solutions.

97 MATHEMATICS AND COMPUTING↗

Impact of temperature and concentration on flow behaviour of reconstituted lactose and protein–rich dairy powders

To help with designing the drying process, this study investigated the flow behaviour of lactose and protein-rich reconstituted dairy powders at 25°C and 50°C. Lactose-rich samples, 50% dried whey (DW) and 60% whey protein concentrate (WPC35) did not follow the Herschel–Bulkley model because of presence of lactose crystals. Reconstituted 50% skim milk powder (SMP) and protein-rich dairy powders exhibited shear-thinning behaviour (n < 0.3). With increasing concentration, whey protein concentrate/isolate (WPC80/WPI) and micellar casein concentrate high-solid dispersions exhibited more shear-thinning behaviour (n < 0.4). Furthermore, understanding shear-thinning behaviour of lactose-rich and protein-rich reconstituted dairy powders will provide basis for optimising drying parameters.

36 MATERIALS SCIENCE↗

Metalorganic chemical vapor deposition-regrown Ga-rich InGaP films on SiGe virtual substrates for Si-based III-V optoelectronic device applications

Ga-rich InGaP materials are attractive applications for yellow-green spectral range optoelectronics such as light-emitting diodes and solar cells on silicon substrate. Bulk, Ga-rich InGaP films grown by metalorganic chemical vapor deposition on SiGe virtual substrates were investigated in the V/III compositional ratio range of 44.3–402 using chamber pressures from 100 to 200 mbar. These films were nominally lattice matched to the SiGe virtual substrate with a bandgap energy of 2.07–2.09 eV at low temperature (10 K). The authors show that the surface morphology of the Ga-rich InGaP films was dependent on the growth conditions, including the V/III gas phase ratio, pressure, and growth rate. By optimizing the growth conditions, the authors achieved improved surface morphologies of the Ga-rich InGaP films. The hillock density of the films produced using a V/III gas phase ratio of 44.3 and 75.4, a growth pressure of 100 mbar, and a growth rate of 0.9 μm/h was about an order of magnitude lower (30.3–50 × 104 cm−2) than that observed using higher V/III gas phase ratios such as 201 and 402. An increase in luminescence efficiency of Ga-rich InGaP materials was observed when the hillock density is lower. The authors discuss the mechanisms of the hillock formation.

Kim, TaeWan↗

Morphological and Surface Structural Changes during Electrochemical Cycling in Li-rich Layered Oxides for Next Generation Li-ion Batteries

Li-rich layered oxides, either as a solid solution or as a nano-composite of layered Li 2 MnO 3 and Li(TM)O 2 (TM=Ni, Co, Mn), draw significant attention as the next-generation cathode materials for high-energy-density Li-ion batteries in electric vehicles. However, there are many issues still unclear, and numerous scientific challenges of these materials that must be overcome to realize their utilization in commercial Li-ion batteries. The first drawback is the irreversible voltage degradation process that limits cycle life. Modified co-precipitation synthesis is introduced to obtain morphology controlled Li-rich material without ammonia addition. This unique design increases meso-structure morphological stability compared with the sample with large secondary particles as proved by Transmission X-ray Microscope. As a result, the voltage decay and capacity loss during long term cycling have been minimized to a large extent. On the other hand, lattice oxygen plays an intriguing role in the electrochemical process of Li-rich material through a reversible redox process as well as an irreversible oxidation with O 2 gas release. To prevent oxygen gas generation, oxygen vacancies have been proposed to form on the surface of the morphology controlled Li-rich layered oxides through the design of a gas-solid interface reaction (GSIR). Dynamic structural changes during the initial two electrochemical cycles of GSIR Li-rich layered oxides are investigated with In operando synchrotron X-ray diffraction (SXRD). Different electrochemical reaction regions dominated by either cations or anions redox are identified in the shifts of the lattice parameters during the first cycle. Changes in lattice parameters, oxygen positions, and microstrain help to explain the lithium de-intercalation mechanism in this class of materials.

Zhang, Minghao↗

ASSOCIATION OF {sup 3}He-RICH SOLAR ENERGETIC PARTICLES WITH LARGE-SCALE CORONAL WAVES

Small, {sup 3}He-rich solar energetic particle (SEP) events have been commonly associated with extreme-ultraviolet (EUV) jets and narrow coronal mass ejections (CMEs) that are believed to be the signatures of magnetic reconnection, involving field lines open to interplanetary space. The elemental and isotopic fractionation in these events are thought to be caused by processes confined to the flare sites. In this study, we identify 32 {sup 3}He-rich SEP events observed by the Advanced Composition Explorer , near the Earth, during the solar minimum period 2007–2010, and we examine their solar sources with the high resolution Solar Terrestrial Relations Observatory ( STEREO ) EUV images. Leading the Earth, STEREO -A has provided, for the first time, a direct view on {sup 3}He-rich flares, which are generally located on the Sun’s western hemisphere. Surprisingly, we find that about half of the {sup 3}He-rich SEP events in this survey are associated with large-scale EUV coronal waves. An examination of the wave front propagation, the source-flare distribution, and the coronal magnetic field connections suggests that the EUV waves may affect the injection of {sup 3}He-rich SEPs into interplanetary space.

79 ASTRONOMY AND ASTROPHYSICS↗

iPTF15eqv: Multiwavelength Exposé of a Peculiar Calcium-rich Transient

The progenitor systems of the class of “Ca-rich transients” is a key open issue in time domain astrophysics. These intriguing objects exhibit unusually strong calcium line emissions months after explosion, fall within an intermediate luminosity range, are often found at large projected distances from their host galaxies, and may play a vital role in enriching galaxies and the intergalactic medium. Here we present multiwavelength observations of iPTF15eqv in NGC 3430, which exhibits a unique combination of properties that bridge those observed in Ca-rich transients and SNe Ib/c. iPTF15eqv has among the highest [Ca ii]/[O i] emission line ratios observed to date, yet is more luminous and decays more slowly than other Ca-rich transients. Optical and near-infrared photometry and spectroscopy reveal signatures consistent with the supernova explosion of a ≲10 M{sub ⊙} star that was stripped of its H-rich envelope via binary interaction. Distinct chemical abundances and ejecta kinematics suggest that the core collapse occurred through electron-capture processes. Deep limits on possible radio emission made with the Jansky Very Large Array imply a clean environment (n ≲ 0.1 cm{sup −3}) within a radius of ∼10{sup 17} cm. Chandra X-ray Observatory observations rule out alternative scenarios involving the tidal disruption of a white dwarf (WD) by a black hole, for masses >100 M {sub ⊙}. Our results challenge the notion that spectroscopically classified Ca-rich transients only originate from WD progenitor systems, complicate the view that they are all associated with large ejection velocities, and indicate that their chemical abundances may vary widely between events.

79 ASTRONOMY AND ASTROPHYSICS↗

The Volumetric Rate of Calcium-rich Transients in the Local Universe

Here, we present a measurement of the volumetric rate of "calcium-rich" optical transients in the local universe, using a sample of three events from the Palomar Transient Factory (PTF). This measurement builds on a detailed study of the PTF transient detection efficiencies and uses a Monte Carlo simulation of the PTF survey. We measure the volumetric rate of calcium-rich transients to be higher than previous estimates: 1.21 -0.39 +1.13 10 -5 events yr -1 Mpc -3 . This is equivalent to 33%-94% of the local volumetric Type Ia supernova rate. This calcium-rich transient rate is sufficient to reproduce the observed calcium abundances in galaxy clusters, assuming an asymptotic calcium yield per calcium-rich event of ~0.05 M ⊙ . As a result, we also study the PTF detection efficiency of these transients as a function of position within their candidate host galaxies. We confirm as a real physical effect previous results that suggest that calcium-rich transients prefer large physical offsets from their host galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗

Origin of Large Meteoritic SiC Stardust Grains in Metal-rich AGB Stars

Stardust grains that originated in ancient stars and supernovae are recovered from meteorites and carry the detailed composition of their astronomical sites of origin. We present evidence that the majority of large (μm-sized) meteoritic silicon carbide (SiC) grains formed in C-rich asymptotic giant branch (AGB) stars that were more metal-rich than the Sun. In the framework of the slow neutron captures (the s process) that occur in AGB stars, the lower-than-solar $^{88}$Sr/$^{86}$Sr isotopic ratios measured in the large SiC grains can only be accompanied by Ce/Y elemental ratios that are also lower than solar and predominately observed in metal-rich barium stars—the binary companions of AGB stars. Such an origin suggests that these large grains represent the material from high-metallicity AGB stars needed to explain the s-process nucleosynthesis variations observed in bulk meteorites. In the outflows of metal-rich, C-rich AGB stars, SiC grains are predicted to be small (≃0.2 μm); large (≃μm-sized) SiC grains can grow if the number of dust seeds is 2–3 orders of magnitude lower than the standard value of 10 -13 times the number of H atoms. We therefore predict that with increasing metallicity, the number of dust seeds might decrease, resulting in the production of larger SiC grains.

79 ASTRONOMY AND ASTROPHYSICS↗

The Gaia-ESO survey: metal-rich bananas in the bulge

We analyze the kinematics of ∼2000 giant stars in the direction of the Galactic bulge, extracted from the Gaia-ESO survey in the region −10{sup ∘}≲ℓ≲10{sup ∘} and −11{sup ∘}≲b≲−3{sup ∘}. We find distinct kinematic trends in the metal-rich ([M/H]>0) and metal-poor ([M/H]<0) stars in the data. The velocity dispersion of the metal-rich stars drops steeply with latitude, compared to a flat profile in the metal-poor stars, as has been seen previously. We argue that the metal-rich stars in this region are mostly on orbits that support the boxy–peanut shape of the bulge, which naturally explains the drop in their velocity dispersion profile with latitude. The metal-rich stars also exhibit peaky features in their line of sight velocity histograms, particularly along the minor axis of the bulge. We propose that these features are due to stars on resonant orbits supporting the boxy–peanut bulge. This conjecture is strengthened through the comparison of the minor axis data with the velocity histograms of resonant orbits generated in simulations of buckled bars. The “banana” or 2:1:2 orbits provide strongly bimodal histograms with narrow velocity peaks that resemble the Gaia-ESO metal-rich data.

79 ASTRONOMY AND ASTROPHYSICS↗

Stability of Fe 2 S and Fe 12 S 7 to 125 GPa; implications for S-rich planetary cores

The Fe-FeS phase relations were explored in the 22–25 wt. % S compositional range using single crystal X-ray diffraction in a laser heated diamond anvil cell. At pressures up to 125 GPa and at high temperatures, Fe 2 S and Fe 12 S 7 were determined to co-crystallise. The novel Fe 12 S 7 compound adopts the Co 12 P 7 structure and Fe 2 S assumes the Fe 2 P-type structure. Applying these results to an Fe-FeS binary phase diagram exposes a complex series of FeS phase assemblages in the 16–25 wt. % S range, whereby minor changes in S content significantly affect the crystallisation sequence of Fe-S rich planetary cores. For core compositions S-rich of the Fe 2 S-Fe 12 S 7 eutectic, the small density difference between solid Fe 12 S 7 and Fe 2 S is likely to result in the formation of a core slush rather than a gravitationally stable inner core. Crystallisation of denser Fe 2 S at eutectic conditions could then result in gravitational settling of an Fe 2 S-rich inner core over time. As the Fe 2 P-type Fe 2 S has previously been identified forming at high temperatures to pressures as low as 22 GPa, the core crystallisation regimes determined here also elucidate that the Martian core sulfur composition must lie on the S-rich side of the Fe-Fe 3 S eutectic or even the S-rich side of the Fe 3 S-Fe 2 S eutectic to maintain a fully molten core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray clusters of galaxies and the luminosity-richness relation

Properties of the nearby clusters of galaxies (distance class 4 or less) identified with X-ray sources are investigated on the basis of Uhuru observations combined with Ariel 5 and OSO 7 results. General properties of the X-ray clusters, such as richness and morphological type, are discussed. X-ray spectra are presented for those clusters for which sufficient Uhuru observations are available. A fundamental relation between the clusters and their richness as defined optically by Abell is observed, such that the class of richness 2 clusters contains relatively more highly luminous X-ray sources as compared with richness 0 and 1 clusters. The observations are shown not to support the previously suggested correlations between X-ray luminosity and Bautz-Morgan or Rood-Shastry morphological type. It is proposed that the richness-luminosity correlation results from the greater number of galaxies available to produce and contain hot intergalactic gas.

Jones, C.↗

Origin of Ca-Al-rich inclusions. II - Sputtering and collisions in the three-ph8se interstellar medium

The theory put forward by Clayton (1977) for the formation of the Ca-Al-rich inclusions within C3 meteorites is extended to an evolutionary history in a three-phase interstellar medium. Widespread supersonic turbulence in the hot interstellar medium is maintained by supernova shock waves, giving rise to heavy sputtering of the refractory dust. Subsequent reaccumulation with varying dust/gas ratios or varying particle sizes produces isotopically fractionated Ca-Al-rich accumulates. It is thought that the Ca-Al-rich inclusions themselves are formed by the following sequence in the solar system: (1) cold accumulation of larger-than-average Ca-Al-rich particles containing supernova condensate cores into macroscopic (approximately 1 cm) Ca-Al-rich agglomerates, probably by sedimentation; and (2) fusion of the supernova condensates into macroscopic minerals by exothermic chemical reactions that begin when the accumulate has been warmed, thereby releasing energy from the unequilibrated forms accumulated from the interstellar medium.

Clayton, D. D.↗