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LiFePO4 was synthesized by a high temperature method and high purity was confirmed by both powder X-ray diffraction and thermal analysis. It can deliver 136Ah/kg, 80% of theoretical capacity at 1mA/cm2 at high cathode load levels at room temperature; 100% capacity can be obtained by raising the temperature to 60°C or reducing the discharge rate to 0.1mA/cm2. The method of carbon addition/coating was not found to be critical, carbon black being as efficient as in situ formed carbon coatings. These materials suffer from a low volumetric energy density, which will seriously impact their possible application. Stabilized layered structures of manganese substituted nickel oxides, such as LiMn0.4Co0.2Ni0.4O2, show a behavior typical of a single phase intercalation reaction, and a reversible capacity of around 180Ah/kg with an upper voltage cut-off of 4.3V. Stabilized δ-structures of vanadium pentoxide show capacities approaching 300Ah/kg, but with a median discharge potential of 2.6V.
From mixed (anatase and rutile) bulk particles, anatase TiO2 nanotubes are synthesized in this study by an alkaline hydrothermal reaction and a consequent annealing at 300–400°C. The physical and electrochemical properties of the TiO2 nanotube are investigated for use as an anode active material for lithium-ion batteries. Upon the first discharge–charge sweep and simultaneous impedance measurements at local potentials, this study shows that interfacial resistance decreases significantly when passing lithium ions through a solid electrolyte interface layer at the lithium insertion/deinsertion plateaus of 1.75/2.0V, corresponding to the redox potentials of anatase TiO2 nanotubes. For an anatase TiO2 nanotube containing minor TiO2(B) phase obtained after annealing at 300°C, the high-rate capability can be strongly enhanced by an isotropic dispersion of TiO2 nanotubes to yield a discharge capacity higher than 150mAhg−1, even upon 100 cycles of 10C-rate discharge–charge operations. This is suitable for use as a high-power anode material for lithium-ion batteries.
A novel electrochemiluminescence (ECL) sensor based on tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)3 2+)/electrospun carbon nanofiber (CNF)/Nafion composite films was demonstrated for the determination of atropine. The voltammetric and ECL behaviors of the presented sensor were investigated. The results indicated that the addition of CNF in the composite films could increase the current and ECL intensity of Ru(bpy)3 2+, which were subjected to diffusion-controlled processes. Under optimal experimental conditions, the proposed ECL sensor exhibited a wide linear range (r = 0.9967) of 1 × 10−7–1 × 10−4 M with a detection limit (S/N = 3) of 1 × 10−7 M for atropine. The relative standard deviation for 1 × 10−5 M atropine is 2.86% (n = 7), and the present ECL sensor displayed outstanding stability. The ECL sensor was also utilized for the determination of atropine in urine samples, and the recovery was in the range of 81%–88%.
The spontaneous conversion of formal residential and commercial buildings into high-density, informal housing is a major policy issue in the inner cities of developing countries. Yet there remains little research material to date analysing the residence dynamics, environmental health and related policy implications of this form of settlement. This paper presents and compares findings from two preliminary studies of informal sub-divided housing in the cities of São Paulo, Brazil, and Johannesburg, South Africa. It points to some of the policy implications of the work, in the light of broader debate on the management of informal settlements, and calls for further research examining this housing form within developing countries.
Herein, we report the synthesis of metallic molybdenum microspheres and hierarchical MoS2 nanostructures by facile template-free solvothermal and hydrothermal approach, respectively. The morphological transition of the Mo microspheres to hierarchical MoS2 nanoflower architectures is observed to be accomplished with change in solvent from ethylenediamine to water. The resultant marigold flower-like MoS2 nanostructures are few layers thick with poor crystallinity while spherical ball-like molybdenum microspheres exhibit better crystalline nature. This is the first report pertaining to the synthesis of Mo microspheres and MoS2 nanoflowers without using any surfactant, template or substrate in hydro/solvothermal regime. It is opined that such nanoarchitectures of MoS2 are useful candidates for energy related applications such as hydrogen evolution reaction, Li ion battery and pseudocapacitors. Inquisitively, metallic Mo can potentially act as catalyst as well as fairly economical Surface Enhanced Raman Spectroscopy (SERS) substrate in biosensor applications.
Transition metal sulfides (TMS) are considered as anode candidates for sodium-ion batteries (SIBs) due to the high theoretical specific capacity and natural abundance. Herein, Co3S4@1T MoS2/NC-L hierarchical nanosheets, in which bimetallic sulfides are integrated into N-doped carbon, has been designed and prepared via calcination of leaf-like Co-ZIF (ZIF-L) precursor followed by hydrothermal sulfuration reaction. When evaluated as anode for SIBs, the Co3S4@1T MoS2/NC-L hierarchical nanosheets offer enhanced pseudocapacitance effect, fast Na+ kinetics in the heterogenous interface of bimetallic sulfides and small polarization, achieving an delightful reversible capacity of 595 mAh g−1 at 0.1 A g−1 and rate capability of 338 mA h g−1 at 5 A g−1. Moreover, the fine structural stability and mutual affinity of bimetallic sulfides under high cutoff voltage hinder the loss of sodium polysulfide during conversion reaction, promoting the long cycling stability of hierarchical nanosheets. Such bimetallic sulfides/N-doped carbon hierarchical nanosheet sheds new light on the construction of efficient anode material for SIBs.
This work concerns the interaction between hydrogen and iron in the cathodic potential region. It was motivated by the need for a better understanding of the hydrogen insertion mechanism in metals. Electrochemical deposits of iron with various thicknesses were carried out on a gold substrate and they were characterized by impedance measurements under hydrogen evolution conditions. The processes occurring at the surface and within the iron films deposited on a gold electrode were studied using various electrochemical techniques. The impedance and voltammetric behaviours were strongly dependent on the film thickness. The main result of this study is that the charge transfer resistance increases with the film thickness. A model of the adsorption–absorption of hydrogen into iron films was proposed. It considered two types of absorbed hydrogen in a sublayer richer in hydrogen than the bulk metal. There, the hydrogen transported in the film coexists with another one coming from a direct absorption mechanism and “trapped” in some sites. The two absorbed hydrogen are reversibly exchanged. The interaction of hydrogen with palladium and iron was compared. It was concluded that for iron, the insertion of hydrogen results from a competition between a one-step direct hydrogen absorption mechanism and the classical two-step indirect penetration in the metal via the adsorbed hydrogen. At the end, a possible explanation of the deep penetration of the direct hydrogen absorption in the metal, detected by the impedance analysis, is proposed. It is based on the imperfections of numerous first layers of the deposited metals on polycrystalline gold.
Tin dioxide (SnO2) is an attractive material for anodes in energy storage devices, because it has four times the theoretical capacity of the prevalent anode material (graphite). The main obstacle hampers SnO2 from practical application is the pulverization problem caused by drastic volume change (∼300%) during lithium-ion insertion or extraction, which would lead to the loss of electrical conductivity, unstable solid-electrolyte interphase (SEI) formation and consequently severe capacity fading in the cycling. Here, we anchored the SnO2 nanocrystals into three dimensional graphene gel network to tackle this problem. As a result of the three dimensional (3-D) architecture, the huge volume change during cycling was tolerated by the large free space in this 3-D construction, resulting in a high capacity of 1090 mAh g−1 even after 200 cycles. What's more, at a higher current density 5 A g−1, a reversible capacity of about 491 mAh g−1 was achieved with this electrode.
The fundamental goal of prosthesis is to achieve optimal levels of performance and enhance the quality of life of amputees. Socket type prostheses have been widely employed despite their known drawbacks. More recently, the advent of osseointegrated prostheses have demonstrated potential to be a better alternative to socket prosthesis eliminating most of the drawbacks of the latter. However, both socket and osseointegrated limb prostheses are prone to superficial infections during use. Infection prone skin lesions from frictional rubbing of the socket against the soft tissue are a known problem of socket type prosthesis. Osseointegration, on the other hand, results in an open wound at the implant-stump interface. The integration of infection sensors in prostheses to detect and prevent infections is proposed to enhance quality of life of amputees. Pathogenic volatiles having been identified to be a potent stimulus, this paper reviews the current techniques in the field of infection sensing, specifically focusing on identifying portable and flexible sensors with potential to be integrated into prosthesis designs. Various sensor architectures including but not limited to sensors fabricated from conducting polymers, carbon polymer composites, metal oxide semiconductors, metal organic frameworks, hydrogels and synthetic oligomers are reviewed. The challenges and their potential integration pathways that can enhance the possibilities of integrating these sensors into prosthesis designs are analysed.
In this work, a high-performance composite catalyst comprised of IrO2 nanoparticles mounted on Co and N co-doped reduced graphene oxide (Co-N-rGO) is designed and successfully prepared for use in a Li-O2 battery. A battery with this catalyst as the cathode demonstrates very high capacity retention ability and cycling stability: it delivered a high reversible capacity of 11,731mAhg−1 after five cycles at 200mAg−1, and after 200 cycles with limited capacity of 600mAhg−1, the battery’s discharge terminal voltage remains over 2V and its energy efficiency still above 65%. Doping with Co and N, along with mounting the IrO2 nanoparticles, greatly enhances the catalyst’s performance. We suggest that its outstanding performance is attributable to the high surface area of rGO, the enhanced oxygen reduction reaction (ORR) activity arising from doping with Co and N, and the high dispersion and great promotion of IrO2 nanoparticles.
Lithium-ion batteries (LIBs) with liquid electrolytes and microporous polyolefin separator membranes are ubiquitous. Though not necessarily an active component in a cell, the separator plays a key role in ion transport and influences rate performance, cell life and safety. As our understanding of separator properties and the interactions between the separator and the electrolyte deepens, it becomes evident that there are opportunities for improving separators to help meet the greater demands that new applications place on LIB technology. Here, we review the impact of the separator structure and chemistry on LIB performance, assess characterization techniques relevant for understanding structure–performance relationships in separator membranes, and provide an outlook on next-generation separator technology. Insights from this Review indicate that LIB performance can be improved by taking into account the interplay of the separator with its surroundings and indicate that, in the future, separators will be designed to play a more active role in LIB operation. Current and emerging characterization techniques will play an important role in guiding this evolution in separator technology.
Postnatal and antenatal anti-D prophylaxis have dramatically reduced maternal sensitisations and cases of rhesus disease in babies born to women with RhD negative blood group. Recent scientific advances mean that non-invasive prenatal diagnosis (NIPD), based on the presence of cell-free fetal DNA in maternal plasma, could be used to target prophylaxis on "at risk" pregnancies where the fetus is RhD positive. This paper provides the first assessment of cost-effectiveness of NIPD-targeted prophylaxis compared to current policies.
We report herein on recent studies related to nonaqueous magnesium electrochemistry and R&D of rechargeable magnesium batteries. Extensive attempts have been made to examine electrolyte systems based on ionic liquids as potential solutions for nonaqueous magnesium batteries. In general, magnesium electrodes are reactive with many imidazolium-based ionic liquids. In those liquids in which Mg electrodes are apparently stable, they develop a blocking passivation. It was possible to develop improved solutions for rechargeable magnesium batteries based on mixtures of THF, tetraglyme (where the high boiling point of the polyether improves the safety features), and complexes based on Lewis acid–Lewis base reactions between AlCl2R and MgR2 or RMgCl. The choice of the type of Lewis base, the R group and the appropriate acid–base ratios enables a reasonable specific conductivity to be obtained, 100% cycling efficiency of Mg electrodes, and a wide electrochemical window, up to 2.4V. This work included rigorous studies by Raman spectroscopy, electron microscopy, ICP, and a variety of electrochemical techniques. In parallel, Mg insertion cathodes based on cubic TiS2, NiS x , NiSSe and CuS x were also investigated.
Objective Investigate the immediate and residual impacts of sleep extension in tactical athletes. Methods A randomized controlled trial (Sleep extension = EXT vs Control = CON) was conducted on 50 (EXT: 20.12 ± 2.01 years vs CON: 19.76 ± 1.09 years) tactical athletes enrolled in the Reserve Officers' Training Corps (ROTC). Participants wore actigraphs for 15 consecutive nights and completed a cognitive/motor battery after seven habitual sleep nights, after four sleep extension nights, and after the resumption of habitual sleep for four nights. The CON group remained on habitual sleep schedules for the entire study. Results During the intervention, the EXT group significantly increased mean sleep time (1.36 ± 0.71 h, p < 0.001). After sleep extension, there were significant between-group differences on the mean score change since baseline in Psychomotor Vigilance Test (PVT) reaction time (p = 0.026), Trail Making Test (TMT) – B time (p = 0.027), standing broad jump (SBJ) distance (p < 0.001), and motivation levels [to perform the cognitive tasks (p = 0.003) and the SBJ (p = 0.009)]; with the EXT group showing a greater enhancement in performance/motivation. After resuming habitual sleep schedules, significant between-group differences on the mean score change since baseline persisted on SBJ distance (p = 0.001) and motivation to perform the SBJ (p = 0.035), with the EXT showing greater enhancement in performance/motivation. Conclusion Increasing sleep duration in military tactical athletes resulted in immediate performance benefits in psychomotor vigilance, executive functioning, standing broad jump distance, and motivation levels. Benefits on motor performance were evident four days after resumption of habitual sleep schedules. Military tactical athletes aiming to optimize their overall performance should consider the impact of longer sleep durations when feasible.
Artemisia capillaris (AC) has been used as an alternative therapy in obesity, atopic dermatitis, and liver diseases through several biological activity including anti-steatotic, antioxidant, and anti-inflammatory activities. Despite its ethnomedicinal benefits, no sufficient background information is available about the long-term safety and genotoxicity of the AC extract. Therefore, the present study was carried out to investigate the 13-week subchronic toxicity and genotoxicity of the AC extract according to the test guidelines published by the Organization for Economic Cooperation and Development. In the 13-week toxicity study using doses of 25, 74, 222, 667, and 2000 mg/kg body weight, oral administration of the AC extract in male and female rats did not result in any significant adverse effects in food/water consumption, body weight, mortality, hematology, serum biochemistry, organ weight and histopathology. Accordingly, the no-observed-adverse-effect level in rats of both genders was established for the AC extract at 2000 mg/kg/day, the highest dose level tested. In addition, the AC extract was not genotoxic in a battery of tests including Ames test, in vitro chromosome aberration assay and in vivo micronucleus assay. In conclusion, we demonstrated that the AC extract is considered as a safe traditional medicine for human consumption.
Calcium zincates are synthesized using ZnO and Ca(OH)2 in different alcohol solutions by the alcohol-thermal method. Through the scanning electron microscopy (SEM), transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) analysis, the as-prepared samples with small particles are well-crystallized. Additionally, the morphologies of as-prepared calcium zincates are distinct in different reaction solvents such as ethanol, isopropanol and n-butanol, and the calcium zincates synthesized in the ethanol and isopropanol solutions have more excellent crystallinity. As the negative electrode materials for Ni–Zn batteries, the electrochemistry properties of calcium zincates are examined by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge–discharge testing techniques. The results imply that calcium zincates synthesized in the ethanol solution have lower polarization and better reversibility. The cycle performance analysis shows the as-prepared calcium zincates have a very greatly improvement in cycle life and discharge capacity compared with other methods. All of the test results show that the calcium zincates synthesized in the ethanol solution exhibit the best electrochemical performances.
The present work describes the preparation and electrochemical characterisation of titanium/iridium(IV) oxide: tantalum pentoxide (Ti/IrO2:Ta2O5) electrodes for vanadium redox flow battery applications. The electrode surface morphology is examined by field-emission scanning electron microscopy, and their electrochemical behaviours are studied by cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. A charge–discharge study has been performed at different current densities using vanadium sulphate as an electrolyte medium (1.7 M V3.5+ and 4 M H2SO4), and as-prepared Ti/IrO2:Ta2O5 and pristine graphite are used as the anode and cathode, respectively. To better understand the behaviour of the electrodes and for comparison, a vanadium redox flow battery is also constructed using graphite as the anode as well as the cathode, and its charge–discharge performance is examined. The electrochemical study revealed that the Ti/IrO2:Ta2O5 electrodes exhibit slightly higher catalytic activity and long-term stability than the graphite electrode in highly concentrated sulphuric acid medium. The Ti/IrO2:Ta2O5 electrodes also exhibit slightly higher energy density (33 Wh L−1) than the graphite electrode (31.5 Wh L−1). However, the energy efficiency of Ti/IrO2:Ta2O5 electrode at 40 mA cm−2 is 81%, which is lower than that of the graphite electrode (86% at 40 mA cm−2).
The reaction mechanism of the new SEI additive 1-Fluoropropane-2-one in combination with the well-known SEI additive vinylene carbonate in propylene carbonate based electrolytes is investigated. Spectroscopic measurements support the proposition that 1-Fluoropropane-2-one is reduced first and that the reduced species then initiate vinylene carbonate decomposition. Cyclic voltammetry shows only a decomposition peak of the additive FA in the first cycle and does not show any evidence for subsequent vinylene carbonate decomposition at lower potential. NMR spectroscopy shows that after one cycle the signal representing the C-F bonds decreases. In situ Raman measurements show that the decomposition of vinylene carbonate occurs in the same potential range as 1-Fluoropropane-2-one, meaning that the VC decomposition is shifted to higher potentials. Finally, XPS measurements demonstrate that this electrolyte with two additives forms a LiF-rich SEI.
We perform X-ray and neutron total scattering measurements on a lithium-rich transition-metal oxide Li1.2Mn0.6Ni0.2O2 with a layered structure as a positive electrode material for a lithium ion battery, in order to reveal local atomic ordering in the samples prepared by different processes. By performing a reverse Monte Carlo modelling using both the real space and reciprocal space data, we can construct three-dimensional atomic configurations, which allows us to extract the quantitative information within and beyond the layers hidden in average structure obtained by crystallography. It is found that Li tends to be surrounded by Mn within the transition-metal layer. Moreover, it is indicated that Ni at the Li layer is preferable around Ni at the transition-metal layer, suggesting that NiO domain is formed. Such a formation of an inactive domain for Li+ diffusion can be suppressed by changing the preparation process, and the improvement of the positive electrode property is confirmed. We can conclude that the real space function obtained by a total scattering measurement is an indispensable tool to detect the formation of the NiO inactive domain, which provides a crucial guideline of preparation process optimization for better positive-electrode property.
A series of novel gel polymer electrolytes (GPEs) based on a co-polymer matrix of methoxy-poly(ethylene glycol) methacrylate (MPEGM) and hexadecal-poly(ethylene glycol) methacrylate (HPEGM) are synthesized in this study using non-volatile tris(methoxypolyethyleneglycol) aluminate ester ((MPEG n )3-Al) as the plasticizer. Their thermal stability and ionic conductivity are studied by differential scanning calorimeter, thermogravimetric analysis and alternating current impedance techniques. The results show that all the synthesized GPEs possess excellent thermal stability and exhibit relatively high ionic conductivity. Among all the synthesized GPEs, one with the composition of 40wt% MPEGM, 10wt% HPEGM and 50wt% (MPEG7)3-Al exhibits the highest ionic conductivity, up to 0.59×10−3 Scm−1 at 30°C when the salt concentration is [Li]:[EO]=1:20. In addition, a coin cell based on this GPE, with LiFePO4 as cathode and metallic lithium as anode shows discharge capacities as high as 146mAhg−1 and 151mAhg−1 when cycled at 30°C and 50°C, respectively, under a current rate of 0.1C.
The purpose of this article is to provide an outlook for future research in semiconductor electrochemistry. A historical perspective is first presented to frame the recent scientific and technological progress that has been made in the field. The remainder of the article provides an overview of two selected research projects at the frontier of photoelectrochemistry. The first example discusses how exploitation of a deliberately nanostructured interface can provide useful enhancements to the kinetics of interfacial charge transfer events and can allow the use of catalysts without suffering concomitant efficiency losses. The second example discusses a model system that is useful for elucidating the interconnections between the chemical modification, electrical properties, and electrochemical behavior of photoelectrode surfaces.