Transition metal dissolution and degradation in nmc811-graphite electrochemical cells

Nickel-rich lithium nickel-manganese-cobalt oxide cathodes, in particular Li(Ni0.8Mn0.1Co0.1)O2 (NMC811), are currently being commercialized as next generation cathode materials, due to their increased capacities compared to current materials. Unfortunately, the higher nickel content has been shown to accelerate cell degradation and a better understanding is needed to maximize cell lifetimes. NMC811/graphite cells were tested under stressed conditions (elevated temperature and cell voltages) to accelerate degradation focusing on transition metal (TM) dissolution from the cathode. Increasing the cell temperature, upper cut-off voltage (UCV) and number of cycles all accelerated capacity fade and diffraction studies showed that under stressed conditions, additional degradation mechanisms beyond lithium loss to the SEI are present. Significant TM dissolution and subsequent deposition on the graphite anode is seen, particularly at stressed conditions. The concentration of TMs in the electrolyte remained invariant with cycling conditions, presumably reflecting the limited solubility of these ions and emphasizing the role that TM deposition on the anode plays in continuing to drive dissolution. Significant deposits of metals from the cell casings and current collectors were also detected at all cycling conditions, indicating that corrosion and metal leaching can be as important as TM dissolution from the active material in some cell formats.We thank Ms. Jennifer Allen, Prof. Mary Ryan and Dr Daniel Abraham for helpful discussions. We thank Stephen Young and Nigel Howard for assistance with the ICP-OES measurements. This work is supported by the Faraday Institution under grant no. FIRG00

Review of the whirligig beetle genus Gyrinus of Venezuela (Coleoptera: Gyrinidae)

The Venezuelan species of the genus Gyrinus Geoffroy, 1762 are reviewed (Gyrinidae: Gyrininae: Gyrinini). The Venezuelan Gyrinus fauna is found to be comprised of nine species distributed among the subgenera Neogyrinus Hatch, 1926 and Oreogyrinus Ochs, 1935, although Gyrinus (Oreogyrinus) colombicus Régimbart, 1883 is known from imprecisely localized and potentially mislabeled specimens and the species presumably does not occur in Venezuela. Three new species are described: G. (Oreogyrinus) vinolentus sp. nov. from the Andes, and G. (Oreogyrinus) iridinus sp. nov. and G. (Neogyrinus) sabanensis sp. nov., from the Guiana Shield region. Two new synonymies are established: G. amazonicus Ochs, 1958 syn. nov. is synonymized with G. guianus Ochs, 1935, and G. racenisi Ochs, 1953 syn. nov. is synonymized with G. ovatus Aubé, 1838. Gyrinus (Oreogyrinus) feminalis Mouchamps, 1957, described from Venezuela from two female syntypes only, is considered as species inquirendum, as the types were not found. For each species a dorsal habitus, illustration of male and female genitalia, and distribution map are provided. A key and checklist for the Venezuelan Gyrinus species is included

Vandetanib-eluting Radiopaque Beads: <i>In vivo</i> Pharmacokinetics, Safety and Toxicity Evaluation following Swine Liver Embolization.

To evaluate the plasma and tissue pharmacokinetics, safety and toxicity following intra-arterial hepatic artery administration of Vandetanib (VTB)-eluting Radiopaque Beads (VERB) in healthy swine. In a first phase, healthy swine were treated with hepatic intra-arterial administration of VERB at target dose loading strengths of 36 mg/mL (VERB36), 72 mg/mL (VERB72) and 120 mg/mL (VERB120). Blood and tissue samples were taken and analysed for VTB and metabolites to determine pharmacokinetic parameters for the different dose forms over 30 days. In a second phase, animals were treated with unloaded radiopaque beads or high dose VTB loaded beads (VERB100, 100 mg/mL). Tissue samples from embolized and non-embolized areas of the liver were evaluated at necropsy (30 and 90 days) for determination of VTB and metabolite levels and tissue pathology. Imaging was performed prior to sacrifice using multi-detector computed tomography (MDCT) and imaging findings correlated with pathological changes in the tissue and location of the radiopaque beads. The peak plasma levels of VTB (C &lt;sub&gt;max&lt;/sub&gt; ) released from the various doses of VERB ranged between 6.19-17.3 ng/mL indicating a low systemic burst release. The plasma profile of VTB was consistent with a distribution phase up to 6 h after administration followed by elimination with a half-life of 20-23 h. The AUC of VTB and its major metabolite N-desmethyl vandetanib (NDM VTB) was approximately linear with the dose strength of VERB. VTB plasma levels were at or below limits of detection two weeks after administration. In liver samples, VTB and NDM VTB were present in treated sections at 30 days after administration at levels above the &lt;i&gt;in vitro&lt;/i&gt; IC &lt;sub&gt;50&lt;/sub&gt; for biological effectiveness. At 90 days both analytes were still present in treated liver but were near or below the limit of quantification in untreated liver sections, demonstrating sustained release from the VERB. Comparison of the reduction of the liver lobe size and associated tissue changes suggested a more effective embolization with VERB compared to the beads without drug. Hepatic intra-arterial administration of VERB results in a low systemic exposure and enables sustained delivery of VTB to target tissues following embolization. Changes in the liver tissue are consistent with an effective embolization and this study has demonstrated that VERB100 is well tolerated with no obvious systemic toxicity

Evaluation of the Liverpool Drink Less Enjoy More intervention

In the UK it is an offence to knowingly sell alcohol to, or purchase alcohol for, a drunk person (Regulated under Section 141 and 142 of the Licensing Act 2003). However, until recent times public awareness, bar server compliance and police enforcement of this legislation has appeared to be low. Critically, UK nightlife environments are often characterised by high levels of intoxication and alcohol-related harms. Excessive alcohol use damages the public’s health, while managing nightlife drunkenness and associated problems such as anti-social behaviour and violence places huge demands on police, local authorities and health services. To reduce such harms an extensive range of policies and interventions have been implemented at local and national levels including high profile policing, changes to licensing laws and environmental measures to improve safety. Whilst there is some evidence to indicate that these measures may contain and manage alcohol-related harms, they do little to reduce levels of intoxication or address harmful and pervasive cultures of nightlife drunkenness. A study conducted in Liverpool in 2013 found that 84% of alcohol purchase attempts by pseudo-intoxicated actors in pubs, bars and nightclubs were successful (i.e. alcohol was sold to the actor; Hughes et al., 2014). Studies conducted elsewhere have suggested that reductions in the service of alcohol to drunks, and associated harms, in nightlife settings can be achieved through the implementation of multi-component interventions that incorporate community mobilisation, enforcement of the laws around the service of alcohol to drunks and responsible bar server training. Thus to address the sale of alcohol to drunks in the city’s nightlife, local partners developed and implemented the multi-component Say No To Drunks pilot intervention. The intervention aimed to: increase awareness of legislation preventing sales of alcohol to drunks; support bar staff compliance with the law; provide a strong deterrence to selling alcohol to drunks; and promote responsible drinking amongst nightlife users. Following an evaluation of Say No To Drunks, the intervention was further refined, broadened and implemented as a second phase in 2015 – rebranded to Drink Less Enjoy More. To inform the continued development of the intervention, the Centre for Public Health at Liverpool John Moores University was commissioned to evaluate the intervention, comparing the results to previous work

Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot.

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated "on-the-fly" re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g. $^{7}$Li and $^{31}$P at 117 and 122MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic $^{7}$Li and $^{31}$P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO$_{4}$; (2) paramagnetic $^{17}$O VT-NMR of the solid oxide fuel cell cathode material La$_{2}$NiO$_{4+δ}$; (3) broadband $^{93}$Nb static NMR of the Li-ion battery material BNb$_{2}$O$_{5}$; and (4) broadband static $^{127}$I NMR of a potential Li-air battery product LiIO$_{3}$. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1-25MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems.This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 655444 (O.P.). D.M.H. acknowledges funding from the Cambridge Commonwealth Trusts. J.L. gratefully acknowledges Trinity College, Cambridge (UK) for funding. K.J.G. gratefully acknowledges funding from the Winston Churchill Foundation of the United States and the Herchel Smith Scholarship. M.B. is the CEO of NMR Service GmbH (Erfurt, Germany), which manufactures the eATM device; M.B. acknowledges funding of the Central Innovation Programme for small and medium-sized enterprises (SMEs; Zentrales Innovationsprogramm Mittelstand, ZIM) of the German Federal Ministry of Economic Affairs and Energy (Bundesministerium für Wirtschaft und Energie, BMWi) under the Grant No. KF 2845501UWF. DFT calculations were performed on (1) the Darwin Supercomputer of the University of Cambridge High Performance Computing Service (http://www.hpc.cam.ac.uk), provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council and (2) the Center for Functional Nanomaterials cluster, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886

Combined laser and atomic force microscope lithography on aluminum: Mask fabrication for nanoelectromechanical systems

A direct-write laser system and an atomic force microscope(AFM) are combined to modify thin layers of aluminum on an oxidizedsilicon substrate, in order to fabricate conducting and robust etch masks with submicron features. These masks are very well suited for the production of nanoelectromechanical systems(NEMS) by reactive ion etching. In particular, the laser-modified areas can be subsequently locally oxidized by AFM and the oxidized regions can be selectively removed by chemical etching. This provides a straightforward means to define the overall conducting structure of a device by laser writing, and to perform submicron modifications by AFMoxidation. The mask fabrication for a nanoscale suspended resonator bridge is used to illustrate the advantages of this combined technique for NEMS

Automated annotation and visualisation of high-resolution spatial proteomic mass spectrometry imaging data using HIT-MAP.

Spatial proteomics has the potential to significantly advance our understanding of biology, physiology and medicine. Matrix-assisted laser desorption/ionisation mass spectrometry imaging (MALDI-MSI) is a powerful tool in the spatial proteomics field, enabling direct detection and registration of protein abundance and distribution across tissues. MALDI-MSI preserves spatial distribution and histology allowing unbiased analysis of complex, heterogeneous tissues. However, MALDI-MSI faces the challenge of simultaneous peptide quantification and identification. To overcome this, we develop and validate HIT-MAP (High-resolution Informatics Toolbox in MALDI-MSI Proteomics), an open-source bioinformatics workflow using peptide mass fingerprint analysis and a dual scoring system to computationally assign peptide and protein annotations to high mass resolution MSI datasets and generate customisable spatial distribution maps. HIT-MAP will be a valuable resource for the spatial proteomics community for analysing newly generated and retrospective datasets, enabling robust peptide and protein annotation and visualisation in a wide array of normal and disease contexts

Earth Radiation Pressure Modelling for Beidou IGSO Satellites

This study shows ERP (Earth Radiation Pressure) is significant for precise orbit determination of BeiDou satellites, systematic error is observable in the orbit products if it is ignored in the orbital dynamics. Through subdividing CERES (Cloud and Earth Radiation Energy System) 1° by 1° earth radiation grid into 6 levels of triangles, a precise and runtime configurable earth radiation model has been obtained. The results reveal that level 4 subdivision can make the relative error of both longwave and shortwave radiation less than 1%. ERP acceleration for BeiDou IGSO satellite(C08) and its effects on orbit have been analyzed through modelling the earth radiation using a box-wing geometry model. The acceleration in radial is about 2-4 times larger than the along track and normal with magnitude 10-10m/s2 . 30-hour orbit prediction shows the 3D RMS error due to ERP is 0.638 m and its maximum can reach 0.9 m

The enduring value of reciprocal illumination in the era of insect phylogenomics: a response to Cai et al. (2020)

Arguably no other group within Coleoptera has received as robust and sustained investigation into their phylogenetic relationships as aquatic beetles. Among this ecological guild, evolutionary relationships of the families within Dytiscoidea, a clade comprising the charismatic diving beetles (Dytiscidae) and their close relatives, have received particular attention. Very recently, four different studies were published investigating the phylogeny of Dytiscoidea, three of which utilized phylogenomic data, the most recent by Cai etal. (2020). Cai et al. (2020) (hereafter CEA) approached investigating theevolutionary relationships among dytiscoid families by reanalysing the transcriptomic dataset of Vasilikopoulos et al. (2019) using different evolutionary models and data trimming regimes. CEAs analyses recovered three different topologies for relationships amongst Dytiscoidea, two of which have been recovered in several previous studies. The primary difference among these topologies is the placement of Hygrobiidae, either as sister to (Dytiscidae (Amphizoidae + Aspidytidae)), sister to Amphizoidae + Aspidytidae, or as sister to Dytiscidae. In CEA, topologies shown in Fig. 1A, C both received maximal (e.g. bootstrap values of 100 and posterior probabilities of 100%) to strong support respectively via their preferred model of evolution. Whereas CEAs recovery of Hygrobiidae sister to Amphizoidae + Aspidytidae was not as strongly supported, Gustafson et al. (2020) recovered this topology primarily with strong to maximal support across all analyses with comprehensive taxon sampling of Dytiscoidea. Rather than treating the three topologies recovered both within their own study and elsewhere as equally viable hypotheses, CEA dismissed the relationships shown in Fig. 1A, B as the result of phylogenetic methodological error, promoting Fig. 1C as their preferred tree because it is consistent with morphology-based views of dytiscoid relationships. Here, we address (i) the manner in which CEA approached reconciling conflicting hypotheses about the evolution of Dytiscoidea; and (ii) the misconception that dytiscoid relationships shown in Fig. 1C are the most consistent with morphology-based views in relation to those of Fig. 1A, B.Fil: Gustafson, Grey T.. University of Kansas; Estados UnidosFil: Miller, Kelly B.. University of New Mexico. Department of Biology; Estados UnidosFil: Michat, Mariano Cruz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Biodiversidad y Biología Experimental y Aplicada. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Biodiversidad y Biología Experimental y Aplicada; ArgentinaFil: Alarie, Yves. Laurentian University. Department of Biology; CanadáFil: Baca, Stephen M.. University of Kansas; Estados UnidosFil: Balke, Michael. Zoologische Staatssammlung Munchen; AlemaniaFil: Short, Andrew E. Z.. University of Kansas; Estados Unido