Revealing lithium-silicide phase transformations in nano-structured silicon-based lithium ion batteries via in situ NMR spectroscopy.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies.K.O acknowledges a research fellowship from Japanese Society for the Promotion of Science (JSPS). E.S acknowledges support by a Marie Curie Intra European Fellowship within the 7th European Community Framework Programme and thanks Churchill College (Cambridge, UK) for a non-stipendiary Raymond and Beverly Sackler Research fellowship. C.J.K and A.E.F acknowledge a research studentship from the Cambridge Nano Science and Technology Doctoral Training Centre (NanoDTC). A.J.M acknowledges the support from the Winton Programme for the Physics of Sustainability. S.H acknowledges funding from ERC grant InsituNANO (project number 279342). C.P.G and C.D thank the Royal Society, and C.P.G thanks European Research Council (ERC). C.P.G. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the U.S. Department of Energy, under Contract DE-AC02-05CH11231, subcontract 6952000.This is the accepted manuscript. The final version is available from Nature Communications at http://www.nature.com/ncomms/2014/140203/ncomms4217/full/ncomms4217.html

Micro-scale investigation of unsaturated sand in mini-triaxial shearing using X-ray CT

peer reviewedThis paper explores the micro characteristics of unsaturated sand in triaxial shearing by using X-ray computed tomography (X-ray CT). To obtain higher resolution, a mini-triaxial set-up is designed in which the sample is miniaturised to 1 cm in diameter and 2 cm long, allowing scans with a pixel size of 9 μm. Samples are sheared in the mini-triaxial set-up at different constant suction levels (therefore, different degree of saturation). In the meanwhile, the samples are scanned by X-ray CT at various deformation stages, about 0, 2, 5, 10 and 15% axial strain. The three-dimensional (3D) reconstructed image is trinarised based on a region growing technique, which gives access to the microstructure of the solid, liquid and air phases. Then, the 3D image is subdivided into representative volume elements, with length ≈3·8D50, which gives local information of degree of saturation and porosity. It is observed that the sample dilates and water drains out during triaxial test under constant suction condition. The local study shows that the porosity increase and water desaturation are more significant in the middle part of the sample, especially for a higher suction value. This work allows the emphasis of the coupling between dilatancy on shearing (highlighted by the evolution of local porosity) and the evolution of the local degree of saturation in unsaturated granular materials

Cationic surfactants for demulsification of produced water from alkaline-surfactant-polymer flooding

In this research, demulsification of produced water (which is an oil-in-water emulsion) from alkaline–surfactant–polymer flooding, containing sodium alkyl sulfate, was evaluated using five different surfactants from the classes of nonionic, amphoteric, and cationic. It was observed that only single-tail cationic surfactants, namely, dodecyltriemthylammonium chloride (DTAC) and alkyltrimethylammonium bromide (ATAB), with a concentration of 1000 ppm, were capable of attaining transparent separated water phases following 3 h separation at room temperature with relative separation efficiencies, determined using fluorescence spectroscopy, of 89.4 and 59%, respectively. However, the cationic surfactant dimethyldioctadecylammonium chloride (DDOAC) could achieve a relative separation efficiency of only 28.4% after 13 days, in contrast to nonionic and amphoteric surfactants that did not reveal any progress in demulsification. Similarly, given the demulsifier concentration of 1000 ppm, only DTAC and ATAB reduced the negative surface charge of oil droplets in the produced water after 3 h separation, and large droplets were formed owing to their coalescence after the addition of the respective demulsifiers as viewed by optical microscopy. The dominant emulsification mechanism is believed to be electrostatic stabilization. Consequently, the proposed demulsification mechanism is the formation/adsorption of cationic–anionic pairs at the oil–water interface. When comparing the demulsification performances of various demulsifying surfactants, although high interfacial activity (low interfacial tension (IFT)) is an essential feature for a demulsifier to be considered effective, it was concluded that lower equilibrium IFT does not necessarily result in superior separation efficiency, and other parameters such as type, tail branch number (i.e., single-tail or double-tail), and purity of surfactant may have profound effects on both separation efficiency and demulsification speed of the emulsion. From the dynamic IFT data, it was realized that DTAC and ATAB caused faster demulsification than DDOAC. The undesirable demulsification performance of DDOAC might have been due to its double-tail structure, which confined its interfacial adsorption. The operational variables, including salinity, pH, and temperature, in the demulsification process by DTAC were optimized with respect to the changes of IFT, and the optimum values were found to be 2 wt %, 7.0, and 35 °C, respectively

Are decision trees a feasible knowledge representation to guide extraction of critical information from randomized controlled trial reports?

<p>Abstract</p> <p>Background</p> <p>This paper proposes the use of decision trees as the basis for automatically extracting information from published randomized controlled trial (RCT) reports. An exploratory analysis of RCT abstracts is undertaken to investigate the feasibility of using decision trees as a semantic structure. Quality-of-paper measures are also examined.</p> <p>Methods</p> <p>A subset of 455 abstracts (randomly selected from a set of 7620 retrieved from Medline from 1998 – 2006) are examined for the quality of RCT reporting, the identifiability of RCTs from abstracts, and the completeness and complexity of RCT abstracts with respect to key decision tree elements. Abstracts were manually assigned to 6 sub-groups distinguishing whether they were primary RCTs versus other design types. For primary RCT studies, we analyzed and annotated the reporting of intervention comparison, population assignment and outcome values. To measure completeness, the frequencies by which complete intervention, population and outcome information are reported in abstracts were measured. A qualitative examination of the reporting language was conducted.</p> <p>Results</p> <p>Decision tree elements are manually identifiable in the majority of primary RCT abstracts. 73.8% of a random subset was primary studies with a single population assigned to two or more interventions. 68% of these primary RCT abstracts were structured. 63% contained pharmaceutical interventions. 84% reported the total number of study subjects. In a subset of 21 abstracts examined, 71% reported numerical outcome values.</p> <p>Conclusion</p> <p>The manual identifiability of decision tree elements in the abstract suggests that decision trees could be a suitable construct to guide machine summarisation of RCTs. The presence of decision tree elements could also act as an indicator for RCT report quality in terms of completeness and uniformity.</p

Delithiation/lithiation behavior of LiNi<inf>0.5</inf>Mn<inf>1.5</inf>O<inf>4</inf> studied by in situ and ex situ ^6,7Li NMR spectroscopy

Delithiation and lithiation behaviors of ordered spinel LiNi0.5Mn1.5O4 and disordered spinel LiNi0.4Mn1.6O4 were investigated by using in situ (in operando) 7Li NMR and ex situ 6Li MAS NMR spectroscopy. The in situ 7Li monitoring of the ordered spinel revealed a clear appearance and subsequent disappearance of a new signal from the well-defined phase Li0.5Ni0.5Mn1.5O4, suggesting the two-phase reaction processes among Li1.0Ni0.5Mn1.5O4, Li0.5Ni0.5Mn1.5O4, and Li0.0Ni0.5Mn1.5O4. Also, for the disordered spinel, Li0.5Ni0.4Mn1.6O4 was identified with a broad distribution in Li environment. High-resolution 6Li MAS NMR spectra were also acquired for the delithiated and lithiated samples to understand the detailed local structure around Li ions. We suggested that the nominal Li-free phase Li0.0Ni0.5Mn1.5O4 can accommodate a small amount of Li ions in its structure. The tetragonal phases Li2.0Ni0.5Mn1.5O4 and Li2.0Ni0.4Mn1.6O4, which occurred when the cell was discharged down to 2.0 V, were very different in the Li environment from each other. It is found that 6, 7Li NMR is highly sensitive not only to the Ni/Mn ordering in LiNi0.5Mn1.5O4 but also to the valence changes of Ni and Mn on charge-discharge process

Systematic Grant and Funding Body Acknowledgment Data for Publications: An Examination of New Dimensions and New Controversies for Bibliometrics

Bibliographic databases are beginning to provide systematic grant and funding body acknowledgement data for the publications they index. This paper considers how this new data might be used for policy purposes and the key issues that are likely to arise in its use. While the attempt to provide this kind of systematic data is in its relative infancy, there is already sufficient information within the WOS database to examine a number of controversies in science studies. This paper considers one such issue, namely the relationship between the number of funding sources acknowledged and the citation impact of publications where a positive relationship has been assumed to exist. Analyses of sets of publications from 2009 from the journals Cell and Physical Review Letters give contrasting results, suggesting that our understanding of the issue of the relationship between the impact of a publication and the number of funding sources which it acknowledges is not fully understood and may be more complicated that previously considered. It is proposed that scientific research findings are packaged by researchers into papers in a variety of ways for a wide variety of purposes. Individual funding quanta from whatever source are not therefore inputs to papers directly; rather, such funding supports a process that has amongst its outcomes, the production of papers