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Hydrothermal reactions between potassium permanganate and vanadyl sulfate have been used to synthesize new forms of vanadium oxides. Depending on the reactant ratios and pH values of the reaction mixtures, two different layered materials have been identified. The first one formed at a pH value of 1.6 has an interlayer distance of 10.90Å and a composition of K0.16Mn0.04V2O4.94·0.14H2O, while the second one formed at pH values higher than 3.0 has an interlayer distance of 9.45Å and a composition of K0.44V2O4.96. Structural analysis indicates that they have a δ-type structure with potassium ions residing in between double sheets of vanadium oxide. The structure and composition of these materials have a profound effect on their charge and discharge properties when used as cathodes in lithium batteries. The sample prepared at a pH value of 2.3 shows best overall performance considering both reversible capacity and cyclability, which is explained with the coexistence of two layered phases in the material. This material has a capacity of over 200mAh/g between 3.6 and 2.2V and retains a capacity of 190mAh/g after 30 cycles. Increase of manganese to vanadium ratio during synthesis leads to a gradual loss of the layered structure and decreased lithium insertion capacity.
The authors find that the Avpr1a gene, encoding the vasopressin-1A receptor, is responsible for strain-dependent pain sensitivity of mice to formalin and capsaicin. In humans, a single nucleotide polymorphism in AVPR1A was found to affect capsaicin pain and desmopressin analgesia. In both species, the effects were male specific and dependent on stress levels at the time of testing.
Novel electrolytes with wide electrochemical potential window and high thermal stability have great potential for aqueous rechargeable lithium-ion batteries (ARLBs). Herein, we report the synthesis of two ionic salts of lithium sulfonylbis(fluorosulfonyl)imide (LiSFSI) and lithium carbonylbis(fluorosulfonyl)imide (LiCFSI) with divalent Li+ for ARLBs. These ionic compounds are the derivatives of monovalent lithium bis(fluorosulfonyl)imide (LiFSI). The LiSFSI and LiCFSI exhibit the kinetic electrochemical stability window of ca. 3.78 and 3.52 V, respectively, which can be further expanded due to the formation of a stable solid electrolyte interface (SEI) layer. While LiFSI exhibits the kinetic electrochemical stability window of ca. 2.22 V without the formation of an SEI layer. Full ARLBs based on LiSFSI and LiCFSI electrolytes with a LiCoO2 cathode and graphite anode can deliver the specific discharge capacity of ca. 113.50 and 95.0 mAh/g, respectively, at 0.1C rate. Whereas, it is ca. 52.53 mAh/g for LiFSI at 0.1C rate. The capacity retention for LiSFSI, LiCFSI, and LiFSI based ARLBs are ca. 97.3, 89.6, and 67.8%, respectively, after 500 cycles. Furthermore, both LiSFSI and LiCFSI reveal much higher thermal stability compared to LiFSI. Thus, the derivatization of conventional ionic compounds is an effective strategy to enhance the battery performance and its lifetime.
Children’s mathematical achievement depends on their domain-specific abilities and their domain-general skills such as executive functions (EFs) and visual-spatial skills (VSS). Research indicates that these two domain-general skills predict mathematical achievement. However, it is unclear whether these skills are differently associated with mathematical achievement across a large age range. The current cross-sectional study answered this question using a large, representative sample aged 5–20 years (N = 1754). EFs, VSS, and mathematical achievement were assessed using the Intelligence and Development Scales–2. Hierarchical regression analyses were computed with EFs and VSS as predictor variables and mathematical achievement as dependent variable. We examined (non-) linear effects and interactions of EFs and VSS with age. Results indicated that EFs and VSS were distinctly associated with mathematical achievement above and beyond effects of age, sex, maternal education, and verbal reasoning. Effects of EFs were linear and age-invariant. Effects of VSS were curvilinear and stronger in adolescents than in children. Our results indicated that EFs and VSS related differently to mathematical proficiency across age, suggesting a varying impact on mathematics across age.
The utilization, dimensioning and operation of hybrid battery systems in all-electric vehicles is addressed in this work. These hybrid battery systems consist of one high power and one high energy lithium-ion battery each. Besides a discussion of the advantages of such a hybridization on battery system level, an insight is given into the dimensioning of the system and related aspects. Moreover, major focus of this paper is dedicated to the energy optimal operation of the hybrid battery system. Therefore, two optimization methods are investigated and applied to the given system and control problem. First the global optimal control solution is derived via dynamic programming. Then a causal controller, which allows for a real-time applicable control of the system, is discussed. A stochastic model of a vehicle's drive missions is introduced and implemented within a stochastic dynamic programming framework. The obtained control laws are applied to vehicle simulations, which include a model of the drivetrain and vehicle chassis. The performance of the controllers is then compared to each other using three driving cycles and two vehicle classes. Finally the causal controller is validated in a hardware-in-the-loop test bench.
Despite clear exacerbation of several skin disorders by stress, the effect of psychologic or exertional stress on human skin has not been well studied. We investigated the effect of three different stressors, psychologic interview stress, sleep deprivation, and exercise, on several dermatologic measures: transepidermal water loss, recovery of skin barrier function after tape stripping, and stratum corneum water content (skin conductance). We simultaneously measured the effects of stress on plasma levels of several stress–response hormones and cytokines, natural killer cell activity, and absolute numbers of peripheral blood leukocytes. Twenty-five women participated in a laboratory psychologic interview stress, 11 women participated in one night of sleep deprivation, and 10 women participated in a 3 d exercise protocol. The interview stress caused a delay in the recovery of skin barrier function, as well as increases in plasma cortisol, norepinephrine, interleukin-1β and interleukin-10, tumor necrosis factor-α, and an increase in circulating natural killer cell activity and natural killer cell number. Sleep deprivation also decreased skin barrier function recovery and increased plasma interleukin-1β, tumor necrosis factor-α, and natural killer cell activity. The exercise stress did not affect skin barrier function recovery, but caused an increase in natural killer cell activity and circulating numbers of both cytolytic T lymphocytes and helper T cells. In addition, cytokine responses to the interview stress were inversely correlated with changes in barrier function recovery. These results suggest that acute psychosocial and sleep deprivation stress disrupts skin barrier function homeostasis in women, and that this disruption may be related to stress-induced changes in cytokine secretion.
Advanced Li-ion batteries with high energy and power density are fast approaching compatibility with automotive demands. While the mechanism of operation of these batteries is well understood, the aging mechanisms are still under investigation. Investigation of aging mechanisms in Li-ion batteries becomes very challenging, as aging does not occur due to a single process, but because of multiple physical processes occurring at the same time in a cascading manner. As the current characterization techniques such as Raman spectroscopy, X-ray diffraction, and atomic force microscopy are used independent of each other they do not provide a comprehensive understanding of material degradation at different length (nm2 to m2) scales. Thus to relate the damage mechanisms of the cathode at mm length scale to micro/nanoscale, data at an intermediate length scale is needed. As such, we demonstrate here the use of thermal diffusivity analysis by flash method to bridge the gap between different length scales. In this paper we present the thermal diffusivity analysis of an unaged and aged cell. Thermal diffusivity analysis maps the damage to the cathode samples at millimeter scale lengths. Based on these maps we also propose a mechanism leading to the increase of the thermal diffusivity as the cells are aged.
Organic cathode materials are promising candidates for a new generation of “green batteries”, since they have low toxicity and can be produced from renewable resources or from oil. Especially suitable are organic redox polymers that can be reversibly oxidized and reduced. Because of their often-insulating nature, however, many redox polymers have limited rate capabilities. Their cycling stabilities, which are of high importance for the long cycle-life of a battery cell, rarely exceed 1000 cycles. Here, we present a new concept for redox polymers as cathode materials, in which the oxidized states are stabilized through π–π interactions between redox-active groups. We found that due to these interactions poly(3-vinyl-N-methylphenothiazine) showed excellent cycling stability (after 10000 cycles at a 10C rate, 93% of the initial capacity was retained) in addition to a high rate capability because of supramolecular hole transport. We propose this concept to be used in the future design of redox polymers for batteries.
Plug-in electric vehicles (PEVs), including plug-in hybrid electric vehicles (PHEVs) and battery electric vehicles (BEVs), have the potential to improve the energy and environmental landscape of personal transportation, but face a hurdle of access to charging infrastructure. Additionally, the types, locations, and quantities of electric vehicle supply equipment (EVSE) that will be required are not well established. This study investigates the charging infrastructure requirements from the perspective of PEV operating cost and BEV feasibility. California was selected as the research region and PEV parameters were selected based on the early deployed vehicles available in the emerging commercial market. To minimize operating cost, an optimal charging strategy based on 24 h travel patterns is proposed. Results indicate that charging time strategy is the most important factor in reducing PEV operating cost while greater numbers of charging locations provide diminishing benefits for PHEVs. Higher charging power capability, combined with an acceptable charging time strategy offer only slight benefits for PHEVs, but charging power is an important factor in increasing BEV functionality and decreasing public charging requirements. The approximation of the electric vehicle supply equipment (EVSE) needed at different types of locations (e.g., home, work place, shopping) is proposed based on an optimal charging strategy.
Equivalent circuit model (EMC) of a high-power Li-ion battery that accounts for both temperature and state of charge (SOC) effects known to influence battery performance is presented. Electrochemical impedance measurements of a commercial high power Li-ion battery obtained in the temperature range 20 to 50°C at various SOC values was used to develop a simple EMC which was used in combination with a non-linear least squares fitting procedure that used thirteen parameters for the analysis of the Li-ion cell. The experimental results show that the solution and charge transfer resistances decreased with increase in cell operating temperature and decreasing SOC. On the other hand, the Warburg admittance increased with increasing temperature and decreasing SOC. The developed model correlations that are capable of being used in process control algorithms are presented for the observed impedance behavior with respect to temperature and SOC effects. The predicted model parameters for the impedance elements R s , R ct and Y 013 show low variance of 5% when compared to the experimental data and therefore indicates a good statistical agreement of correlation model to the actual experimental values.
In recent years, storage of thermal energy has become a very important topic in many engineering applications and has been the subject of a great deal of research activity. This paper reviews the thermal energy storage technologies suitable for building applications with a particular interest in heat storage materials. The paper provides an insight into recent developments on materials, their classification, their limitations and possible improvements for their use in buildings. Three major thermal energy storage modes (sensible heat, latent heat, thermochemical heat) are described emphasizing the main characteristics of the most suitable heat storage materials for each.
In this study, we report the cost-effective and simple synthesis of carbon-coated α-MnO2 nanoparticles (α-MnO2@C) for use as cathodes of aqueous zinc-ion batteries (ZIBs) for the first time. α-MnO2@C was prepared via a gel formation, using maleic acid (C4H4O4) as the carbon source, followed by annealing at low temperature of 270°C. A uniform carbon network among the α-MnO2 nanoparticles was observed by transmission electron microscopy. When tested in a zinc cell, the α-MnO2@C exhibited a high initial discharge capacity of 272mAh/g under 66mA/g current density compared to 213mAh/g, at the same current density, displayed by the pristine sample. Further, α-MnO2@C demonstrated superior cycleability compared to the pristine samples. This study may pave the way for the utilizing carbon-coated MnO2 electrodes for aqueous ZIB applications and thereby contribute to realizing high performance eco-friendly batteries.
This study examines the effects of the addition of Mn and LmNi4.1Al0.25Mn0.3Co0.65 (Lm: lanthanum-rich mischmetal) alloy on the electrochemical characteristics of body centered cubic (BCC) type Ti0.32Cr0.43−x Mn x V0.25 (x =0–0.08) alloys as negative electrode (anode) materials for nickel–metal-hydride (Ni-MH) batteries. The activation behaviour and discharge capacity of the BCC alloys are improved significantly by ball-milling with LmNi4.1Al0.25Mn0.3Co0.65 alloy because this AB5 alloy acts as a path for hydrogen on the surface of the BCC alloy. Among the Mn-substituted alloys, a Ti0.32Cr0.38Mn0.05V0.25 alloy ball-milled with the AB5 alloy yields the greatest discharge capacity of 340mAhg−1. In addition, compared with the alloy without Mn, the Mn-substituted alloys exhibit a lower plateau pressure for hydrogen, a better hydrogen-storage capacity in the pressure–composition isotherms and faster surface activation.
Lithium is a highly interesting metal, in part due to the increasing interest in lithium-ion batteries. Several recent studies have used different methods to estimate whether the lithium production can meet an increasing demand, especially from the transport sector, where lithium-ion batteries are the most likely technology for electric cars. The reserve and resource estimates of lithium vary greatly between different studies and the question whether the annual production rates of lithium can meet a growing demand is seldom adequately explained. This study presents a review and compilation of recent estimates of quantities of lithium available for exploitation and discusses the uncertainty and differences between these estimates. Also, mathematical curve fitting models are used to estimate possible future annual production rates. This estimation of possible production rates are compared to a potential increased demand of lithium if the International Energy Agency’s Blue Map Scenarios are fulfilled regarding electrification of the car fleet. We find that the availability of lithium could in fact be a problem for fulfilling this scenario if lithium-ion batteries are to be used. This indicates that other battery technologies might have to be implemented for enabling an electrification of road transports.
Organic expanders function in the negative electrode of lead–acid batteries to promote the development of fine crystal sponge lead upon formation and to preserve this high surface area structure by preventing coarsening of crystals upon cycling. Organic expanders also serve to protect the negative active material from passivation during discharge or on open circuit by preventing the formation of an impervious non-conducting film of lead sulfate. The deleterious effect of a high temperature service environment on the life of the lead–acid battery and the negative electrode is well known. In this paper, we investigate the effect of Vanisperse A organic expander content on the capacity and life of the negative electrode of flooded lead–acid SLI batteries designed to be negative electrode limiting. The low rate capacity and cold cranking performance of batteries designed to be negative electrode limiting remained essentially unchanged upon increasing the organic expander dosage from 0.25 to 0.50% on weight of lead oxide in a negative mixture. Battery life, however, when tested according to the SAE J240 protocol, increased 25% at 41°C, and 20% at 75°C. When tested according to the SAE J2185 protocol at 50°C, battery life increased 15%. No adverse effects were observed. This work shows that increasing the Vanisperse content has a beneficial effect on the high temperature service life of the negative electrode.
For next generation Li-ion batteries, advanced electrode materials with high energy densities are mightily important issue. Since the partial oxidation of Sn with Li2O to form SnO x was demonstrated upon delithiation in SnO2 anode, the additional conversion reaction has contributed that the theoretical capacity of SnO2 can be extended from 783 to 1494 mAh g−1. Herein, with the design of additional conversion reaction, we discuss key factors for high electrochemical performances of the SnO2 anodes through comparative analysis between nano-structured mesoporous SnO2 and conventional bulk SnO2, based on synchrotron radiation-based techniques, quantitative analysis of extended X-ray absorption fine structure spectra, and bond strength calculation. In this way, we demonstrate that the mesoporous SnO2 has a nano-engineered structure with the weakened Sn-O bond strength for inducing the enhanced reversible conversion reaction as well as the facilitated electrochemical reaction, and a void structure for relieving the severe volume changes during lithiation/delithiation. Consequently, excellent electrochemical performance through the additional reversible conversion reaction is obtained in the mesoporous SnO2. Insight from this research enables important advance in the development of metal oxide-based anode materials by making irreversible reaction reversible, providing a realizable strategy for the design and creation of high-energy storage devices.
LiFePO4 and LiFePO4/C microspheres are successfully synthesized via facile co-precipitation in an elevated temperature oil bath. Their morphologies and structures are investigated by X-ray diffractometer, scanning electron microscope and transmission electron microscope. LiFePO4/C microspheres are uniform between 2 and 4μm in diameter and composed of nanoparticles from 30 to 80nm in size. Nanoparticles are coated by a thin nano-carbon layer and imbedded into three-dimensional nano-carbon networks. LiFePO4/C microspheres exhibit a high tap density (1.82gcm−3), deliver large reversible discharge capacity of 165mAhg−1 at 0.1C rate, excellent rate capability of 106mAhg−1 at 50C rate, and capacity retention over 98% after 20 cycles even applied 50C rate. Therefore, the material is a potential candidate for high-power lithium ion batteries.
Fuel cells have been touted as a long-lasting power supply for mobile devices, but have proved to be a promise unfulfilled — so far. Reports in the international trade and technical press are now predicting that 2006 will be the year such fuel cells start to be recognized as a potential replacement for batteries in portable electronics applications. This article looks at the technology, and shows why the mobile fuel cell market should be taken seriously.
Switchgrass (Panicum virgatum L.) grown for biomass feedstock production has the potential to increase soil C sequestration, and soil CO2 flux in grassland is an important component in the global C budget. The objectives of this study were to: (1) determine the effects of N fertilization and harvest frequency on soil CO2 flux, soil microbial biomass carbon (SMBC), and potentially mineralizable carbon (PMC); and (2) evaluate the relationship of soil CO2 flux with soil temperature, soil moisture, SMBC, and PMC. Two N rates (0 and 224kgha−1) were applied as NH4NO3 and cattle (Bos Taurus L.) manure. Switchgrass was harvested every year at anthesis or alternate years at anthesis. The data were collected during growing season (May–October) 2001–2004 on switchgrass-dominated Conservation Reserve Program (CRP) land in east-central South Dakota, USA. Manure application increased soil CO2 flux, SMBC, and PMC during the early portion of the growing season compared with the control, but NH4NO3 application did not affect soil CO2 flux, SMBC, and PMC. However, seasonal variability of soil CO2 flux was not related to SMBC and PMC. Estimated average soil CO2 fluxes during the growing periods were 472, 488, and 706g CO2–Cm−2 for control, NH4NO3–N, and manure-N plots, respectively. Switchgrass land with manure application emitted more CO2, and approximately 45% of the C added with manure was respired to the atmosphere. Switchgrass harvested at anthesis decreased soil CO2 flux during the latter part of the growing season, and flux was lower under every year harvest treatment than under alternate years harvest. Soil temperature was the most significant single variable to explain the variability in soil CO2 flux. Soil water content was not a limiting factor in controlling seasonal CO2 flux.
The Prussian blue and polypyrrole nanocomposite (PB–PPy) was synthesised by a facile spontaneous self-assembly (SA) procedure through the layering of multiple sequential absorptions of FeCl3–K3[Fe(CN)6] and pyrrole. The morphology of PB–PPy nanocomposite was rough and irregular, whereas the PB nanocubes (used as experimental control) had a diameter of about 40 nm which were formed using the SA method. The intercalation pseudocapacitive mechanism occurs when potassium ions were inserted to the PB framework. The electrochemical behaviour and areal capacitance of PB–PPy were compared with pristine PB. The “knee frequency” was only present in the Nyquist plot of PB–PPy. The result revealed that the PPy significantly improved the capacitance of pristine PB and this made PB–PPy as a promising candidate for supercapacitors. The specific areal capacitance of PB–PPy was at least ten times higher than pristine PB.
We investigated the relationship between physical properties and electrochemical performances for Li1+y Ni x Co1−2x Mn x O2 positive active materials. The improvement of rate capability by excess Li was related to the increased electrical conductivity that was accompanied by Ni3+ increase. Electrochemical impedance measurements indicated that the charge-transfer resistance decreases with increased excess Li content (electrical conductivity) for Li1+y Ni x Co1−2x Mn x O2. The value of charge-transfer resistance was compared with the simulated value by the equivalent circuits’ model considering the volume resistivity of positive active material.