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The LiMn1.5Ni0.5O4 spinel is an attractive cathode candidate for next generation lithium-ion batteries as it offers high power capability with an operating voltage of ∼4.7 V and a capacity of ∼135 mA h g−1. However, its commercialization is plagued by severe capacity fade, particularly at elevated temperatures, in full cells employing a graphite anode. This perspective article provides an overview of the recent developments on understanding various factors that influence the electrochemical performance of the high-voltage spinel cathodes. The factors include the degree of cation ordering, Mn3+ content, morphology, and surface planes/compositions in contact with the electrolyte, which are influenced by synthesis and annealing conditions as well as cation doping. For example, samples with a {111} family of surface planes show superior performance. Recent magnetic measurements and examination of discharge profiles below 3 V have become valuable to get a more precise measure of the degree of cation ordering. Also, surface modifications and electrolyte additives have shown marginal gains. Although acceptable performances have been obtained in half-cells with a metallic lithium anode, capacity fade is seen in full cells with a graphite anode due to metal dissolution at the high operating voltage of 4.7 V and Li+ consumption by the steadily forming solid–electrolyte interphase (SEI) layer promoted by Mn/Ni deposition on the graphite surface. Based on the current understanding, future directions are pointed out.
The design of new homes includes many safety features intended to protect occupiers from injury or ill health within the home, however the effectiveness of these primary intervention measures is likely to be affected by user behaviour. This study examined the interaction between user activity and dwelling design and how this might affect health and safety. It aimed to identify how people use features within new homes and how this may limit the protection afforded by building design, codes and regulations. Forty, home-based, semi-structured, in-depth interviews and home inspections were conducted with individuals recently inhabiting a new home. A range of behaviours were reported in relation to building features including fire doors, pipes and cables, and loft access, which may lead to increased risk of injury or ill-health. For example, occupiers described interfering with the self-closing mechanisms on fire doors and drilling into walls without considering the location of services. They also reported knowingly engaging in unsafe behaviour when accessing the loft, increasing their risk of falls. The accounts suggest that designers and builders need to give greater consideration to how occupier behaviour interacts with building features so that improvements in both design and occupier education can lead to improved health and safety.
The Sn-based intermetallic compounds possess a high specific energy density, but their most important challenge to be used as anodes in lithium ion batteries consists in the mechanical fatigue caused by volume change during lithium intercalation and extraction processes. The current paper presents a facile procedure to prepare macroporous Sn–Co alloy film electrode through a colloidal crystal template method together with electroplating on a Ni-coated Cu sheet substrate. The structure and electrochemical properties of the macroporous Sn–Co alloy films were examined by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and galvanostatic cycling. The results illustrated that the macroporous Sn–Co alloy film electrode can deliver a reversible capacity as high as 610mAhg−1 up to 75th cycle. In comparison with the Sn–Co alloy film directly deposited on Ni-coated Cu sheet substrate, the macroporous structure of the Sn–Co alloy electrode prepared by the present procedure has enhanced significantly the capacity and the cyclic performance. It has demonstrated that the macroporous structure has played an important role, in addition to the alloying effect, to overcome the effect of volume expansion during charge/discharge cycling of Sn-based alloy anodes.
The accurate diagnosis of tuberculosis (TB) in children remains challenging. A myriad of common childhood diseases can present with similar symptoms and signs, and differentiating between exposure and infection, as well as infection and disease can be problematic. The paucibacillary nature of childhood TB complicates bacteriological confirmation and specimen collection is difficult. In most instances intrathoracic TB remains a clinical diagnosis. TB infection and disease represent a dynamic continuum from TB exposure with/without infection, to subclinical/incipient disease, to non-severe and severe disease. The clinical spectrum of intrathoracic TB in children is broad, and the classification of clinical, radiological, endoscopic, and laboratory findings into recognized clinical syndromes allows a more refined diagnostic approach in order to minimize both under- and over-diagnosis. Bacteriological confirmation can be improved significantly by collecting multiple, high-quality specimens from the most appropriate source. Mycobacterial testing should include traditional smear microscopy and culture, as well as nucleic acid amplification testing. A systematic approach to the child with recent exposure to TB, or with clinical and radiological findings compatible with this diagnosis, should allow pragmatic classification as TB exposure, infection, or disease to facilitate timely and appropriate management. It is important to also assess risk factors for TB disease progression and to undertake follow-up evaluations to monitor treatment response and ongoing evidence supporting a TB, or alternative, diagnosis.
The development of efficient and cheap anode materials for the utilization in the oxygen evolution reaction (OER) is essential for energy-conversion technologies. In this study, hierarchically porous Co3O4 architectures with honeycomb-like structures are synthesized by employing cobalt-based zeolitic imidazolate framework (ZIF-67-Co) as metal source and sacrificial template. After a simple one-step calcination process, the ZIF-67-Co precursor can be chemically transformed into the Co3O4 architectures with abundant porosity and oxygen vacancy. These easily obtained and earth-abundant Co3O4 architectures present high performance toward the electrochemical water splitting for evolving molecular oxygen, affording a small OER onset potential, large anodic current and long-term durability in 0.1 M KOH solution, which are comparable to the electroactive noble- and transition-metal oxygen evolution catalysts previously reported. These merits suggest that the ZIF-derived Co3O4 architectures are promising electrocatalysts for OER from water splitting.
The purpose of this paper is to review the requirement for potentially scarce or hazardous metals used in a wide range of electric vehicle batteries, in order to provide datasets that could be used as a basis for a variety of assessments of electric vehicles and batteries, such as life-cycle assessments (LCA) and material availability assessments. It is an explicit objective to make the calculations and assumptions transparent so that the datasets can easily be recalculated with different assumptions. We investigate the requirement for metals of nine types of batteries: Li-metal(V), Li-ion(Mn, Ni and Co), NaNiCl, NiMH(AB2 and AB5), NiCd and PbA, which contain seven potentially scarce or hazardous metals/group of metals: lithium, nickel, cobalt, vanadium, cadmium, lead and mischmetal (rare-earth elements). We provide datasets for both near-term and improved technology of the requirement for metals per kWh battery as well as per battery electric vehicle.
Heterogeneous electrochemical phenomena, such as (photo)electrochemical water splitting to generate hydrogen using semiconductors and/or electrocatalysts, are driven by the accumulated charge carriers and thus the interfacial electrochemical potential gradients that promote charge transfer. However, measurements of the “surface” electrochemical potential during operation are not generally possible using conventional electrochemical techniques, which measure/control the potential of a conducting electrode substrate. Here we show that the nanoscale conducting tip of an atomic force microscope cantilever can sense the surface electrochemical potential of electrocatalysts in operando. To demonstrate utility, we measure the potential-dependent and thickness-dependent electronic properties of cobalt (oxy)hydroxide phosphate (CoPi). We then show that CoPi, when deposited on illuminated haematite (α-Fe2O3) photoelectrodes, acts as both a hole collector and an oxygen evolution catalyst. We demonstrate the versatility of the technique by comparing surface potentials of CoPi-decorated planar and mesoporous haematite and discuss viability for broader application in the study of electrochemical phenomena.
The aryl hydrocarbon receptor (AhR) is a well-known ligand-activated cytoplasmic transcription factor that contributes to cellular responses against environmental toxins and carcinogens. AhR is activated by a range of structurally diverse compounds from the environment, microbiome, natural products, and host metabolism, suggesting that AhR possesses a rather promiscuous ligand binding site. Increasing studies have indicated that AhR can be activated by a variety of endogenous ligands and induce the expression of a battery of genes. AhR regulates a variety of physiopathological events, including cell proliferation, differentiation, apoptosis, adhesion and migration. These new roles have expanded our understanding of the AhR signalling pathways and endogenous metabolites interacting with AhR under homeostatic and pathological conditions. Recent studies have demonstrated that AhR is linked to cardiovascular disease (CVD), chronic kidney disease (CKD) and renal cell carcinoma (RCC). In this review, we summarize gut microbiota-derived ligands inducing AhR activity in patients with CKD, CVD, diabetic nephropathy and RCC that may provide a new diagnostic and prognostic approach for complex renal damage. We further highlight polyphenols from natural products as AhR agonists or antagonists that regulate AhR activity. A better understanding of structurally diverse polyphenols and AhR biological activities would allow us to illuminate their molecular mechanism and discover potential therapeutic strategies targeting AhR activation.
Magnetorotational Instability (MRI) has long been considered a possible mechanism to transport angular momentum allowing fast accretion in astrophysical objects, but its standard form with a vertical magnetic field has never been experimentally verified. The authors present an experimental demonstration of a spring-mass analogue of the standard MRI using water as working fluid and a spring to mimic the action of magnetic fields.
Dysfunction in the neuronal nicotinic acetylcholine receptor (nAChR) system has been implicated in the pathophysiology of schizophrenia, and it has been postulated that treatments that increase nAChR activity may improve symptoms of the disorder. We investigated the effects of the acetylcholinesterase inhibitor and allosteric nAChR modulator, galantamine, on cognitive performance and clinical symptoms when added to a stable antipsychotic medication regimen in nonsmoking outpatients with schizophrenia in a double-blind, placebo-controlled, parallel-group design. Participants were randomized to receive either galantamine (n =10) up to 32 mg/day or identical placebo (n = 10) for 8 weeks and completed a cognitive battery at baseline and week 8 and clinical scales at baseline, week 4 and week 8. The primary outcome measure was attentional performance as measured by the d' measure in the Continuous Performance Test — Identical Pairs (CPT-IP) Version. Contrary to our hypothesis, galantamine treatment was associated with inferior performance on the CPT-IP, on the three-card Stroop task, and on the Letter–Number Span task without reordering. Galantamine had no effect on clinical symptoms. In summary, galantamine treatment, at a dose of 32 mg/day, was well tolerated but was not effective as an adjunctive treatment for cognitive deficits in stable nonsmokers with schizophrenia.
Age-related muscle and fat mass (FM) changes are ethnicity specific. We aimed to develop a cut-point for the muscle mass component of sarcopenia for black South African (SA) women, and to assess its predictive value, in comparison to established cut-points, to identify functional ability among older black SA women.
The structural evolution of Li3V2(PO4)3/C upon cycling in different potential ranges was studied via XRD. The results reveal that the repeated charge/discharge processes would cause the loss of crystallinity and irreversible expansion of unit cell volume, both of which are related to the applied upper limit of potential. The highest degree of the crystallinity loss and irreversible expansion of unit cell volume of the Li3V2(PO4)3/C sample cycled in the range of 3.0-4.8V is considered to be partially responsible for the worst cycling performance among the three operating potential regions. On the contrary, no marked expansion of unit cell volume is observed when the upper limit of potential is extended from 4.3V to 4.6V. Accordingly, the Li3V2(PO4)3/C sample cycled in 3.0-4.6V delivers extra 17-37 mAh g−1 specific capacity over that of 3.0-4.3V with reasonable cycling stability. Therefore, the potential range of 3.0-4.6V would be the best operating potential region for the practical applications of Li3V2(PO4)3.
The reactivity between charged Li[NixMnyCoz]O2 (NMC, with x + y + z = 1, x:y:z = 1:1:1 (NMC111), 4:4:2 (NMC442), 5:3:2 (NMC532), 6:2:2 (NMC622) and 8:1:1 (NMC811)) and traditional carbonate-based electrolytes at elevated temperatures was systematically studied using accelerating rate calorimetry (ARC). The ARC results showed that the upper cut-off potential and NMC composition strongly affect the thermal stability of the various NMC grades when traditional carbonate-based electrolyte was used. Although higher cut-off potential and higher Ni content can help increase the energy density of lithium ion cells, these factors generally increase the reactivity between charged NMC and electrolyte at elevated temperatures. It is hoped that this report can be used to help guide the wise selection of NMC grade and upper cut-off potential to achieve high energy density Li-ion cells without seriously compromising cell safety.
Research on the cathode catalysts of lithium–oxygen (Li–O2) batteries is one of the most important branches to commercialize these batteries to overcome the sluggish kinetics during both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). In this study, a high performance catalyst based on a bimetallic Pt–Cu alloy is investigated for Li–O2 batteries using first-principles calculation. The theoretical prediction shows that the Pt–Cu alloy is much more effective than the pure Pt according to the electrochemical performance. In particular, the effectiveness of the catalytic property is maximized in the case of the PtCu (111) surface which greatly reduces the large overpotentials of the original Li–O2 batteries during the OER/ORR. It is identified for the first time that the charge overpotentials are affected mainly by the inherent surface charge character of the alloy catalyst. It is observed that the more negatively charged PtCu (111) surface can act as a weakly positively charged surface for the adsorption of Li–O intermediates and thus result in weak ionic bonding of the intermediates on the surface. As a result, the dominant factor improving the catalytic performance is clearly demonstrated, providing insight into the design of an efficient catalyst for Li–O2 battery technologies.
The paper presents the practical results of measuring different types of lithium iron phosphate (LiFePO4) and lithium titanate (LTO) batteries during the loading by charging/discharging cycles, with particular emphasis on cell heating and thermal capacity of the entire system. Finally, it presents recommendations on the operating conditions of LiFePO4 cells and batteries.
Overcharge of lithium-ion batteries can lead to the deposition of lithium ions on the surface of graphite electrodes. The phenomenon of lithium deposition causes reduced electrochemical performance and presents safety concerns for lithium-ion batteries in high-power applications. This study presents a technique using neutron radiography (NR) for in situ visualization of the effects of overcharge in a graphite/NCA (LiNi0.8Co0.15Al0.05O2) lithium-ion cell. Patterns of deposition of solid material on the surface of the graphite electrode observed in the radiographs were confirmed by direct observation of the electrode. Inductively coupled plasma mass spectrometry was used to verify the elemental contents of the deposited material. NR is shown to be a promising tool for the study of lithium-ion batteries in high-power applications.
The purpose of this study was to assess the influence of age on thalamic deep brain stimulation (DBS) in essential tremor (ET). Tremor, cognition, mood and adverse events in patients with thalamic DBS for ET were evaluated in 26 consecutive patients with established standardized methods for tremor and cognition. Twelve patients <70 and 14 patients ≥70 years were included and followed for 2 years. Clinical outcomes did not differ significantly. DBS seems to be safe and effective for ET independent of age.
Hierarchical chestnut-like manganese cobalt oxide (MnCo2O4) nanoneedles (NNs) are successfully grown on nickel foam using a facile and cost-effective hydrothermal method. High resolution TEM image further verifies that the chestnut-like MnCo2O4 structure is assembled by numerous 1D MnCo2O4 nanoneedles, which are formed by numerous interconnected MnCo2O4 nanoparticles with grain diameter of ∼10 nm. The MnCo2O4 electrode exhibits high specific capacitance of 1535 F g−1 at 1 A g−1 and good rate capability (950 F g−1 at 10 A g−1) in a 6 M KOH electrolyte. An asymmetric supercapacitor is fabricated using MnCo2O4 NNs on Ni foam (MnCo2O4 NNs/NF) as the positive electrode and graphene/NF as the negative electrode. The device shows an operation voltage of 1.5 V and delivers a high energy density of ∼60.4 Wh kg−1 at a power density of ∼375 W kg−1. Moreover, the device exhibits an excellent cycling stability of 94.3% capacitance retention after 12000 cycles at 30 A g−1. This work demonstrates that hierarchical chestnut-like MnCo2O4 NNs could be a promising electrode for the high performance energy storage devices.
Electrochemical hydrogen charge/discharge measurements of the as-milled alloys were carried out under galvanostatic conditions. It was found that with increased milling time the discharge capacity increased and reached a value of 230 mAh g−1 for the 30 h milled sample, which is a substantially higher value than those published for this alloy composition. The cycle life of the alloy with the finest nanostructure is, however, shorter compared to the coarser nanostructures.
A capacitive deionization process utilizing flow-electrodes (FCDI) was designed and evaluated for use in seawater desalination. The FCDI cell exhibited excellent removal efficiency (95%) with respect to an aqueous NaCl solution (salt concentration: 32.1 g L−1), demonstrating that the FCDI process could effectively overcome the limitations of typical CDI processes.
This paper reports on the electrochemistry of a new series of layered manganese oxide cathodes for lithium-ion cells. The layered structure is stabilized by the partial substitution of the manganese by chromium and lithium atoms and by the partial or complete oxidation of the manganese to the +4 oxidation state. The series covers the range of compositions Li x Cr y Mn2−y O4+z for which 2.2<x<4, 0<y<2 and z≥0.
Lithium vanadium oxide has been synthesized as an anode material for lithium ion batteries by spray pyrolysis technique. The precursor prepared by spray pyrolysis is sintered at 1000°C under 10% H2/Ar atmosphere. Highly crystallized hexagonal lithium vanadate, Li1+x VO2, is obtained without any impurities. The product has mean particle size of 7–8μm. Lattice parameters of as-prepared powders vary largely according to Li/V ratio. The powder having the lowest c/a ratio shows the largest discharge capacity. Optimum x value is 0.2 in the view point of the discharge capacity (294mAhg−1) and the cycle retention (>90%, after 25 cycles). Structural change of as-prepared lithium vanadate is investigated by ex situ X-ray diffraction analysis on charged electrodes at various state of charge (SOC). Lithium vanadate undergoes two step phase transition during charging process and its main peak gets broader as the charge state gets higher. This peak broadening is explained by the breaking down of particles at high SOC.
The ionic liquid 1-allyl-1-methylpyrrolidinium chloride was investigated as an additive to an ethylmagnesium bromide Grignard solution, for use as an advanced electrolyte in rechargeable Mg batteries. Electrochemical studies showed that the addition of the ionic liquid significantly enhanced the anodic limit of the Grignard solution by about 1V and improved the coulombic efficiency and the kinetics of Mg deposition-stripping reactions on the negative electrode. We have also demonstrated that the Grignard solution containing the ionic liquid works well as an electrolyte in a prototype cell consisting of a Mo6S8 Chevrel phase cathode and a Mg metal anode, where the original Grignard electrolyte does not function properly.
A novel three-dimensional (3D) Co3O4@Co(OH)2 hybrid nanostructure is synthesized by using two-step hydrothermal and electrodeposition methods. The composite can be employed as an efficient electrode of a high-performance supercapacitor. Scanning electron microscopy and high-resolution transmission electron microscopy images show that Co(OH)2 nanosheets can grow both in the space and on the tops of Co3O4 nanotubes. In comparison with the sole Co3O4 nanotubes and Co(OH)2 nanosheets, the hybrid Co3O4@Co(OH)2 electrode with a naturally formed nanostructure exhibits much improved battery-type performances in a 3molL−1 KOH electrolyte solution, as evidenced by the high specific capacity of 1876 Cg−1 at a current density of 5mAcm−2. A good retention capability is also demonstrated, 83.1% of initial capacity value is maintained after 1000 cycles at a current density of 25mAcm−2. The observed high performances of Co3O4@Co(OH)2 hybrid electrode with the 3D nanostructure make it attractive for the development of high-efficiency electrochemical energy storage devices.
Contrasting results have been reported concerning the association of a splice-site polymorphism (rs10774671) in OAS1 with multiple sclerosis (MS). We analysed two OAS1 regions encompassing alternatively spliced exons. While the region carrying the splice-site variant is neutrally evolving, a signature of long-standing balancing selection was observed across an alternative exon 7. Analysis of variants in this exon identified an insertion/deletion polymorphism (rs11352835, A/−) that originates predicted products with distinct C termini. This variant is located along the major branch of the haplotype genealogy, suggesting that it may represent the selection target. A case/control study for MS indicated that rs11352835 is associated with disease susceptibility (for an allelic model with the deleted allele predisposing to MS, OR 1.27, 95% CI 1.072–1.513, p = 0.010). No association was found between rs10774671 and MS. As the two SNPs are in linkage disequilibrium in Europeans, the previously reported association between rs10774671 and MS susceptibility might be driven by rs11352835, possibly explaining the contrasting results previously observed for the splice-site polymorphism. Thus, we describe a novel susceptibility variant for MS in OAS1 and show that population genetic analyses can be instrumental to the identification of selection targets and, consequently, of functional polymorphisms with an effect on phenotypic traits.