Thermal stress-induced charge and structure heterogeneity in emerging cathode materials

Nickel-rich layered oxide cathode materials are attractive near-term candidates for boosting the energy density of next generation lithium-ion batteries. The practical implementation of these materials is, however, hindered by unsatisfactory capacity retention, poor thermal stability, and oxygen release as a consequence of structural decomposition, which may have serious safety consequences. The undesired side reactions are often exothermic, causing complicated electro-chemo-mechanical interplay at elevated temperatures. In this work, we explore the effects of thermal exposure on chemically delithiated LiNi0.8Mn0.1Co0.1O2 (NMC-811) at a practical state-of-charge (50% Li content) and an over-charged state (25% Li content). A systematic study using a suite of advanced synchrotron radiation characterization tools reveals the dynamics of thermal behavior of the charged NMC-811, which involves sophisticated structural and chemical evolution; e.g. lattice phase transformation, transition metal (TM) cation migration and valence change, and lithium redistribution. These intertwined processes exhibit a complex 3D spatial heterogeneity and, collectively, form a valence state gradient throughout the particles. Our study sheds light on the response of NMC-811 to elevated temperature and highlights the importance of the cathode's thermal robustness for battery performance and safety

Probing 5f-state configurations in URu2Si2 with U L3-edge resonant x-ray emission spectroscopy

Resonant x-ray emission spectroscopy (RXES) was employed at the U L3 absorption edge and the La1 emission line to explore the 5f occupancy, nf, and the degree of 5f orbital delocalization in the hidden order compound URu2Si2. By comparing to suitable reference materials such as UF4, UCd11, and alpha-U, we conclude that the 5f orbital in URu2Si2 is at least partially delocalized with nf = 2.87 +/- 0.08, and does not change with temperature down to 10 K within the estimated error. These results place further constraints on theoretical explanations of the hidden order, especially those requiring a localized f2 ground state.Comment: 11 pages,7 figure

Hammerhead, an ultrahigh resolution ePix camera for wavelength-dispersive spectrometers

Wavelength-dispersive spectrometers (WDS) are often used in synchrotron and FEL applications where high energy resolution (in the order of eV) is important. Increasing WDS energy resolution requires increasing spatial resolution of the detectors in the dispersion direction. The common approaches with strip detectors or small pixel detectors are not ideal. We present a novel approach, with a sensor using rectangular pixels with a high aspect ratio (between strips and pixels, further called "strixels"), and strixel redistribution to match the square pixel arrays of typical ASICs while avoiding the considerable effort of redesigning ASICs. This results in a sensor area of 17.4 mm x 77 mm, with a fine pitch of 25 $\mu$m in the horizontal direction resulting in 3072 columns and 176 rows. The sensors use ePix100 readout ASICs, leveraging their low noise (43 e$^-$, or 180 eV rms). We present results obtained with a Hammerhead ePix100 camera, showing that the small pitch (25 $\mu$m) in the dispersion direction maximizes performance for both high and low photon occupancies, resulting in optimal WDS energy resolution. The low noise level at high photon occupancy allows precise photon counting, while at low occupancy, both the energy and the subpixel position can be reconstructed for every photon, allowing an ultrahigh resolution (in the order of 1 $\mu$m) in the dispersion direction and rejection of scattered beam and harmonics. Using strixel sensors with redistribution and flip-chip bonding to standard ePix readout ASICs results in ultrahigh position resolution ($\sim$1 $\mu$m) and low noise in WDS applications, leveraging the advantages of hybrid pixel detectors (high production yield, good availability, relatively inexpensive) while minimizing development complexity through sharing the ASIC, hardware, software and DAQ development with existing versions of ePix cameras.Comment: 8 pages, 6 figure

High-resolution x-ray-emission study of 1s4p and 1s3d two-electron photoexcitations in Kr

High-energy-resolution photoexcited KN2,3 x-ray-emission measurements were carried out on krypton with the excitation energy tuned around the 1s4p and 1s3d double-excitation thresholds. Comprehensive two-dimensional resonant inelastic x-ray-scattering maps were recorded for the range of excitation and emission energies corresponding to both types of double excitations. The double-excitation signal could be clearly resolved from the dominant 1s ionization signal. The latter was subtracted from the measured maps, yielding isolated 1s4p and 1s3d photoexcitation spectra. Both two-electron excitation spectra are well described by a model spectrum built of consecutive bound-bound discrete transitions and shake-up and shake-off channels giving precise energies and intensities of the corresponding contributions. The obtained results are compared with other existing experimental values based on x-ray-absorption measurements and theoretical predictions

Multiconfigurational nature of 5f orbitals in uranium and plutonium intermetallics

Uranium and plutonium's 5f electrons are tenuously poised between strongly bonding with ligand spd-states and residing close to the nucleus. The unusual properties of these elements and their compounds (eg. the six different allotropes of elemental plutonium) are widely believed to depend on the related attributes of f-orbital occupancy and delocalization, for which a quantitative measure is lacking. By employing resonant x-ray emission spectroscopy (RXES) and x-ray absorption near-edge structure (XANES) spectroscopy and making comparisons to specific heat measurements, we demonstrate the presence of multiconfigurational f-orbital states in the actinide elements U and Pu, and in a wide range of uranium and plutonium intermetallic compounds. These results provide a robust experimental basis for a new framework for understanding the strongly-correlated behavior of actinide materials.Comment: 30 pages, concatenated article and supporting information, 10 figure

Base-accelerated degradation of nanosized platinum electrocatalysts

In the pursuit of a hydrogen economy, extensive research has been directed at developing acidic and alkaline hydrogen fuel cells. Such fuel cells often utilize platinum-based catalysts. These materials have been studied extensively in acidic conditions but not in alkaline ones. This focus on acidic systems creates a marked knowledge gap, since recent studies indicate that carbon-supported platinum (Pt/C) electrocatalysts degrade more rapidly in bases than in acids. Addressing this gap, the present work investigates Pt/C degradation at pH 2 and pH 12 using electrochemistry, transmission electron microscopy (TEM), and in situ X-ray absorption spectroscopy (XAS). TEM and XAS reveal accelerated Pt/C degradation at high pH levels, which results in increased Ostwald ripening, Smoluchowski agglomeration, and nanoparticle detachment. These processes are driven by platinum-catalyzed carbon corrosion and the dissolution and redeposition of platinum nanoparticles. Although these processes take place at both low and high pH levels, basic conditions accelerate the degradation. Base-enhanced Pt dissolution and redeposition was assessed in further detail, revealing an oxidation onset reduction of 100 mV in the base; however, there were no significant differences between undissolved Pt oxidation in acid and in base. The results suggest that soluble Pt oxidation products are stabilized in the base instead. These conclusions are important for translating acidbased literature to alkaline conditions.Catalysis and Surface Chemistr

L-Edge Spectroscopy of Dilute, Radiation-Sensitive Systems Using a Transition-Edge-Sensor Array

We present X-ray absorption spectroscopy and resonant inelastic X-ray scattering (RIXS) measurements on the iron L-edge of 0.5 mM aqueous ferricyanide. These measurements demonstrate the ability of high-throughput transition-edge-sensor (TES) spectrometers to access the rich soft X-ray (100-2000eV) spectroscopy regime for dilute and radiation-sensitive samples. Our low-concentration data are in agreement with high-concentration measurements recorded by conventional grating-based spectrometers. These results show that soft X-ray RIXS spectroscopy acquired by high-throughput TES spectrometers can be used to study the local electronic structure of dilute metal-centered complexes relevant to biology, chemistry and catalysis. In particular, TES spectrometers have a unique ability to characterize frozen solutions of radiation- and temperature-sensitive samples.Comment: 19 pages, 4 figure

Improved electrocatalytic activity of Pt on carbon nanofibers for glucose oxidation mediated by support oxygen groups in Pt perimeter

Support effects in supported metal catalysts are well studied for thermocatalytic reactions, but less studied for electrocatalytic reactions. Here, we prepared a series of Pt supported on carbon nanofiber catalysts which vary in their Pt particle size and the content of oxygen groups on the surface of the CNF. We show that the activity of these catalysts for electrocatalytic glucose oxidation relates linearly with the content of support oxygen groups. Since the electronic state of Pt (XAS) and Pt surface structure (CO-stripping) were indistinguishable for all materials, we conclude that sorption effects of glucose play a crucial role in catalytic activity. This was further confirmed by establishing a relation between the annulus of the Pt particles and the activity.</p

Adoption of Instant Messaging Technologies by University Students

The main objective of this paper is to better understand the nature and patterns of students’ socialization patterns in relation to the adoption of Instant Messaging (IM) systems. A model based on the Extended Planned Behavior Theory (EPBT) was applied to a sample of 80 students of software engineering at the University of New South Wales, Australia. Based on the EPBT model, a questionnaire was administered to these students. A number of key concepts were identified in relation to the students’ adoption of IM. It was also found that students use IM to support a number of task-related purposes such as collaborating with their classmates about group work and assignments, as well as for scheduling and coordinating meetings and significant results were obtained

Bioturbating animals control the mobility of redox-sensitive trace elements in organic-rich mudstone

Bioturbating animals modify the original mineralogy, porosity, organic content, and fabric of mud, thus affecting the burial diagenetic pathways of potential hydrocarbon source, seal, and reservoir rocks. High-sensitivity, synchrotron rapid scanning X-ray fluorescence elemental mapping reveals that producers of phycosiphoniform burrows systematically partition redox-sensitive trace elements (i.e., Fe, V, Cr, Mn, Co, Ni, Cu, and As) in fine-grained siliciclastic rocks. Systematic differences in organic carbon content (total organic carbon >1.5 wt%) and quality (D13Corg~0.6‰) are measured between the burrow core and host sediment. The relative enrichment of redox-sensitive elements in the burrow core does not correlate with significant neo-formation of early diagenetic pyrite (via trace metal pyritization), but is best explained by physical concentration of clay- and silt-sized components. A measured loss (~-15%) of the large-ionic-radius elements Sr and Ba from both burrow halo and core is most likely associated with the release of Sr and Ba to pore waters during biological (in vivo) weathering of silt- to clay-sized lithic components and feldspar. This newly documented effect has significant potential to inform the interpretation of geochemical proxy and rock property data, particularly from shales, where elemental analyses are commonly employed to predict reservoir quality and support paleoenvironmental analysis