Correlative electrochemical acoustic time-of-flight spectroscopy and X-ray imaging to monitor the performance of single-crystal and polycrystalline NMC811/Gr lithium-ion batteries

LiNixMnyCozO2 (NMC) electrodes typically consist of anisotropic single-crystal primary particles aggregated to form polycrystalline secondary particles. Electrodes composed of polycrystalline NMC particles have a comparatively high gravimetric capacity and good rate capabilities but do not perform as well as single crystal equivalents in terms of volumetric energy density and cycling stability. This has prompted research into well-dispersed single-crystalline NMC products as an alternative solution for high-energy-density batteries. Here, for the first time known to the authors, electrochemical acoustic time-of-flight (EA-ToF) spectroscopy has been shown to be effective in distinguishing between Li-ion batteries composed of either single-crystal NMC811 (SC-NMC811) or polycrystalline NMC811 (PC-NMC811) electrodes. Cells composed of PC-NMC811 electrodes had a higher degree of gas evolution compared to cells containing SC-NMC811 electrodes. Cells composed of PC-NMC811 electrodes also underwent larger changes in the acoustic signal's time-of-flight (ToF) during constant current cycling at a range of C-rates indicating expansion, fracture or dislocation of the reflective interfaces inside the cell. In addition, X-ray computed tomography (X-ray CT) has been used to confirm significant morphological differences between SC-NMC811 electrodes and PC-NMC811 electrodes including the electrode's particle size distribution (PSD) that is suggested to have an effect on acoustic signal interaction with these electrode interfaces

Quantifying landscape-level methane fluxes in subarctic Finland using a multiscale approach

Journal ArticleQuantifying landscape-scale methane (CH4) fluxes from boreal and arctic regions, and determining how they are controlled, is critical for predicting the magnitude of any CH4 emission feedback to climate change. Furthermore, there remains uncertainty regarding the relative importance of small areas of strong methanogenic activity, vs. larger areas with net CH4 uptake, in controlling landscape-level fluxes. We measured CH4 fluxes from multiple microtopographical subunits (sedge-dominated lawns, interhummocks and hummocks) within an aapa mire in subarctic Finland, as well as in drier ecosystems present in the wider landscape, lichen heath and mountain birch forest. An intercomparison was carried out between fluxes measured using static chambers, up-scaled using a high-resolution landcover map derived from aerial photography and eddy covariance. Strong agreement was observed between the two methodologies, with emission rates greatest in lawns. CH4 fluxes from lawns were strongly related to seasonal fluctuations in temperature, but their floating nature meant that water-table depth was not a key factor in controlling CH4 release. In contrast, chamber measurements identified net CH4 uptake in birch forest soils. An intercomparison between the aerial photography and satellite remote sensing demonstrated that quantifying the distribution of the key CH4 emitting and consuming plant communities was possible from satellite, allowing fluxes to be scaled up to a 100 km2 area. For the full growing season (May to October), ~ 1.1-1.4 g CH4 m-2 was released across the 100 km2 area. This was based on up-scaled lawn emissions of 1.2-1.5 g CH4 m-2, vs. an up-scaled uptake of 0.07-0.15 g CH4 m-2 by the wider landscape. Given the strong temperature sensitivity of the dominant lawn fluxes, and the fact that lawns are unlikely to dry out, climate warming may substantially increase CH4 emissions in northern Finland, and in aapa mire regions in general.This work was carried out within the Natural Environment Research Council (NERC) funded Arctic Biosphere Atmosphere Coupling at Multiple Scales (ABACUS) project (a contribution to International Polar Year 2007_2008) plus NERC small grant NE/F010222/1 awarded to RB and BH. We are grateful for the support of the staff at the Kevo Subarctic Research Institute, to David Sayer for operation and maintenance of the eddy covariance apparatus, and to Lorna English for helping with the analysis of the CH4 samples. We also thank the NERC Field Spectroscopy Facility for support in ground data collection for the remote sensing analysis. Finally, we wish to express our gratitude to two anonymous reviewers whose comments and suggestions substantially improved the manuscript

Identifying the Origins of Microstructural Defects Such as Cracking within Ni‐Rich NMC811 Cathode Particles for Lithium‐Ion Batteries

The next generation of automotive lithium‐ion batteries may employ NMC811 materials; however, defective particles are of significant interest due to their links to performance loss. Here, it is demonstrated that even before operation, on average, one‐third of NMC811 particles experience some form of defect, increasing in severity near the separator interface. It is determined that defective particles can be detected and quantified using low resolution imaging, presenting a significant improvement for material statistics. Fluorescence and diffraction data reveal that the variation of Mn content within the NMC particles may correlate to crystallographic disordering, indicating that the mobility and dissolution of Mn may be a key aspect of degradation during initial cycling. This, however, does not appear to correlate with the severity of particle cracking, which when analyzed at high spatial resolutions, reveals cracking structures similar to lower Ni content NMC, suggesting that the disconnection and separation of neighboring primary particles may be due to electrochemical expansion/contraction, exacerbated by other factors such as grain orientation that are inherent in such polycrystalline materials. These findings can guide research directions toward mitigating degradation at each respective length‐scale: electrode sheets, secondary and primary particles, and individual crystals, ultimately leading to improved automotive ranges and lifetimes

Weather in stellar atmosphere: the dynamics of mercury clouds in alpha Andromedae

The formation of long-lasting structures at the surfaces of stars is commonly ascribed to the action of strong magnetic fields. This paradigm is supported by observations of evolving cool spots in the Sun and active late-type stars, and stationary chemical spots in the early-type magnetic stars. However, results of our seven-year monitoring of mercury spots in non-magnetic early-type star alpha Andromedae show that the picture of magnetically-driven structure formation is fundamentally incomplete. Using an indirect stellar surface mapping technique, we construct a series of 2-D images of starspots and discover a secular evolution of the mercury cloud cover in this star. This remarkable structure formation process, observed for the first time in any star, is plausibly attributed to a non-equilibrium, dynamical evolution of the heavy-element clouds created by atomic diffusion and may have the same underlying physics as the weather patterns on terrestrial and giant planets.Comment: 10 pages, 2 figures; to be published in Nature Physic

Hiring expert consultants in e-healthcare: an analytics-based two sided matching approach

Very often in some censorious healthcare scenario, there may be a need to have some expert consultancies (especially by doctors) that are not available in-house to the hospitals. Earlier, this interesting healthcare scenario of hiring the expert consultants (mainly doctors) from outside of the hospitals had been studied with the robust concepts of mechanism design with money and mechanism design without money. In this paper, we explore the more realistic two sided matching market in our healthcare set-up. In this, the members of the two participating communities, namely the patients and the doctors are revealing the strict preference ordering over the members of the opposite community for a stipulated amount of time. We assume that the patients and doctors are strategic in nature. With the theoretical analysis, we demonstrate that the TOMHECs, that results in the stable allocation of doctors to the patients, satisfies the several economic properties such as strategy-proof-ness (or truthfulness) and optimality. Further, the analytically based analysis of our proposed mechanisms i.e. RAMHECs and TOMHECs are carried out on the ground of the expected distance of the allocation done by the mechanisms from the top most preference. The proposed mechanisms are also validated with the help of exhaustive experiments.Peer ReviewedPostprint (author's final draft

The Interaction Properties of the Human Rab GTPase Family – A Comparative Analysis Reveals Determinants of Molecular Binding Selectivity

Rab GTPases constitute the largest subfamily of the Ras protein superfamily. Rab proteins regulate organelle biogenesis and transport, and display distinct binding preferences for effector and activator proteins, many of which have not been elucidated yet. The underlying molecular recognition motifs, binding partner preferences and selectivities are not well understood.Comparative analysis of the amino acid sequences and the three-dimensional electrostatic and hydrophobic molecular interaction fields of 62 human Rab proteins revealed a wide range of binding properties with large differences between some Rab proteins. This analysis assists the functional annotation of Rab proteins 12, 14, 26, 37 and 41 and provided an explanation for the shared function of Rab3 and 27. Rab7a and 7b have very different electrostatic potentials, indicating that they may bind to different effector proteins and thus, exert different functions. The subfamily V Rab GTPases which are associated with endosome differ subtly in the interaction properties of their switch regions, and this may explain exchange factor specificity and exchange kinetics.We have analysed conservation of sequence and of molecular interaction fields to cluster and annotate the human Rab proteins. The analysis of three dimensional molecular interaction fields provides detailed insight that is not available from a sequence-based approach alone. Based on our results, we predict novel functions for some Rab proteins and provide insights into their divergent functions and the determinants of their binding partner selectivity

In vivo measurement of bending stiffness in fracture healing

BACKGROUND: Measurement of the bending stiffness a healing fracture represents a valid variable in the assessment of fracture healing. However, currently available methods typically have high measurement errors, even for mild pin loosening. Furthermore, these methods cannot provide actual values of bending stiffness, which precludes comparisons among individual fractures. Thus, even today, little information is available with regards to the fracture healing pattern with respect to actual values of bending stiffness. Our goals were, therefore: to develop a measurement device that would allow accurate and sensitive measurement of bending stiffness, even in the presence of mild pin loosening; to describe the course of healing in individual fractures; and help to evaluate whether the individual pattern of bending stiffness can be predicted at an early stage of healing. METHODS: A new measurement device has been developed to precisely measure the bending stiffness of the healing fracture by simulating four-point-bending. The system was calibrated on aluminum models and intact tibiae. The influence of pin loosening on measurement error was evaluated. The system was tested at weekly intervals in an animal experiment to determine the actual bending stiffness of the fracture. Transverse fractures were created in the right tibia of twelve sheep, and then stabilized with an external fixator. At ten weeks, bending stiffness of the tibiae were determined in a four-point-bending test device to validate the in-vivo-measurement data. RESULTS: In-vivo bending stiffness can be measured accurately and sensitive, even in the early phase of callus healing. Up to a bending stiffness of 10 Nm/degree, measurement error was below 3.4% for one pin loose, and below 29.3% for four pins loose, respectively. Measurement of stiffness data over time revealed a significant logarithmic increase between the third and seventh weeks, whereby the logarithmic rate of change among sheep was similar, but started from different levels. Comparative measurements showed that early individual changes between the third and fourth weeks can be used as a predictor of bending stiffness at seven weeks (r = 0.928) and at ten weeks (r = 0.710). CONCLUSION: Bending stiffness can be measured precisely, with less error in the case of pin loosening. Prediction of the future healing course of the individual fracture can be assessed by changes from the third to the fourth week, with differences in stiffness levels. Therefore, the initial status of the fracture seems to have a high impact on the individual healing course

QTL analysis of measures of mouse home-cage activity using B6/MSM consomic strains

The activity of mice in their home cage is influenced greatly by the cycle of light and dark. In addition, home-cage activity shows remarkable time-dependent changes that result in a prominent temporal pattern. The wild-derived mouse strain MSM/Ms (MSM) exhibits higher total activity in the home cage than does C57BL/6 (B6), a commonly used laboratory strain. In addition, there is a clear strain difference in the temporal pattern of home-cage activity. This study aimed to clarify the genetic basis of strain differences in the temporal pattern of home-cage activity between MSM and B6. Through the comparison of temporal patterns of home-cage activity between B6 and MSM, the pattern can be classified into five temporal components: (1) resting phase, (2) anticipation phase, (3) 1st phase, (4) 2nd phase, and (5) 3rd phase. To identify quantitative trait loci (QTLs) involved in these temporal components, we used consomic strains established from crosses between B6 and MSM. Five consomic strains, for Chrs 2T (telomere), 3, 4, 13, and 14, showed significantly higher total activity than B6. In contrast, the consomic strains of Chrs 6C (centromere), 7T, 9, 11, and 15 were less active than B6. This indicates that multigenic factors regulate the total activity. Further analysis showed an impact of QTLs on the temporal components of home-cage activity. The present data showed that each temporal component was regulated by different combinations of multigenic factors, with some overlap. These temporal component-related QTLs are important to understand fully the genetic mechanisms that underlie home-cage activity