149 research outputs found
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
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 <sup>6,7</sup>Li 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
Bridging Effective Stress and Soil Water Retention Equations in Deforming Unsaturated Porous Media: A Thermodynamic Approach
A multi-disciplinary perspective on emergent and future innovations in peer review [version 2; referees: 2 approved]
Peer review of research articles is a core part of our scholarly communication system. In spite of its importance, the status and purpose of peer review is often contested. What is its role in our modern digital research and communications infrastructure? Does it perform to the high standards with which it is generally regarded? Studies of peer review have shown that it is prone to bias and abuse in numerous dimensions, frequently unreliable, and can fail to detect even fraudulent research. With the advent of web technologies, we are now witnessing a phase of innovation and experimentation in our approaches to peer review. These developments prompted us to examine emerging models of peer review from a range of disciplines and venues, and to ask how they might address some of the issues with our current systems of peer review. We examine the functionality of a range of social Web platforms, and compare these with the traits underlying a viable peer review system: quality control, quantified performance metrics as engagement incentives, and certification and reputation. Ideally, any new systems will demonstrate that they out-perform and reduce the biases of existing models as much as possible. We conclude that there is considerable scope for new peer review initiatives to be developed, each with their own potential issues and advantages. We also propose a novel hybrid platform model that could, at least partially, resolve many of the socio-technical issues associated with peer review, and potentially disrupt the entire scholarly communication system. Success for any such development relies on reaching a critical threshold of research community engagement with both the process and the platform, and therefore cannot be achieved without a significant change of incentives in research environments
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
Consequences on water retention properties of double-porosity features in a compacted silt
De Novo
The crystal structure of form 4 of the drug 4-[4-(2-adamantylcarbamoyl)-5-tert-butyl-pyrazol-1-yl]benzoic acid is determined using a protocol for NMR powder crystallography at natural isotopic abundance combining solid-state 1H NMR spectroscopy, crystal structure prediction, and density functional theory chemical shift calculations. This is the first example of NMR crystal structure determination for a molecular compound of previously unknown structure, and at 422 g/mol this is the largest compound to which this method has been applied so far
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