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In situ differential electrochemical mass spectrometry (DEMS) was used to study the SEI film formation on highly crystalline TIMREX® SLX50 graphite negative electrodes during the first electrochemical lithium insertion using either 1M LiPF6 in ethylene carbonate (EC) with either dimethyl carbonate (DMC) or propylene carbonate (PC) as co-solvent. In the case of the propylene and ethylene carbonate containing electrolyte, DEMS measurements indicate strong formation of ethylene and propylene gas below 0.75V versus Li/Li+, which does not decrease at lower cell potential and in the subsequent charge/discharge cycles. Whereas for the dimethyl carbonate containing electrolyte, ethylene gas formation could be observed already above 1V versus Li/Li+. Post mortem scanning electron microscopy (SEM) studies of the electrodes show strong exfoliation of the graphite electrode when they are discharged in the ethylene/propylene carbonate electrolyte, indicating the formation of an unstable SEI layer. The addition of vinylene carbonate (VC) as a film forming additive significantly decreases the gas formation at the graphite electrode in the propylene carbonate containing electrolyte. The exfoliation was suppressed by the vinylene carbonate additive. We show that the combination of different in situ and ex situ methods can provide new useful information about the passivation process of graphite, as well as the solid electrolyte interphase layer formed, during the first electrochemical insertion of lithium into graphite negative electrode materials.
Oxidative stress-mediated genotoxicity of wastewaters taken from two different cities, Saharanpur (SWW) and Aligarh (AWW), were compared with a battery of short-term assays namely the Allium cepa genotoxicity test, the plasmid-nicking assay, and the Ames fluctuation test. Both test-water samples – when used undiluted – increased the frequency of chromosomal abnormalities and/or micronuclei and alterations in the mitotic index of root cells of Allium cepa. Bridges and fragmentation of the chromosome were the predominant effects of the Saharanpur water sample while the Aligarh sample induced mainly chromosome fragmentation. Single- and double-strand breaks were also observed in plasmid DNA treated with these test wastewaters. The plasmid-nicking assay performed on SWW resulted in linearization of plasmid DNA when 18μl was tested (in a total reaction volume of 20μl). However, with the same amount of AWW, all three forms of plasmid, viz. supercoiled, open circular and linear were observed. Supplementation with specific scavengers of reactive oxygen species (ROS) caused a significant decline in mutagenicity of test-water samples in all the tests, pointing at oxidative stress as the mediator of the observed genotoxicity. The role of heavy metals in the AWW-induced oxidative stress and that of phenolics in SWW cannot be ruled out.
Lithium–sulfur (LiS) batteries could potentially revolutionize the rechargeable battery market due to their high energy density and low cost. However, low active material utilization, electrode volumetric expansion and a high rate of capacity fade due to the dissolution of lithium polysulfide intermediates in the liquid electrolyte are the main challenges facing further LiS battery development. Here, we enhanced LiS batteries active material utilization and decreased the volumetric expansion by using the lithium/dissolved polysulfide configuration. Moreover, a novel class of cathode materials, Titanium Nitride (TiN), was developed for polysulfide conversion reactions. The surface chemical environment of the TiN has been investigated by X-ray photoelectron spectroscopy (XPS) analysis. The existence of STiN bonding at the cathode electrode surface was observed, which indicates the strong interactions between TiN and polysulfides. Therefore, the TiN electrode retains the sulfur species on the cathode surface, minimizing the active material and surface area loss and consequently, improves the capacity retention. The resultant cells demonstrated a high initial capacity of 1524 mAh g−1 and a good capacity retention for 100 cycles at a C/10 current rate.
Vanadium oxides (V3O7) have been used as electrode materials for supercapacitor applications because of its multiple oxidation states. V3O7 nanoparticles were coated on reduced graphene oxide (rGO) from a peroxovanadate-rGO composite by thermal microexplosive decomposition method. These V3O7 decorated rGO were made composite with the flexible multi redox conducting polymer (Polyaniline). The performance of the composite materials as electrode for supercapacitors was analyzed in a 3-electrode cell, obtaining a specific capacitance of about 579 F g−1 at 0.2 A g−1 specific current. Cycling stability is one of the main barriers noticed in V3O7, which limits the practical performance of supercapacitors. This is overcome by modifying V3O7 with rGO and polyaniline composites which produces good electrical contact resulting in higher capacitances and enhanced cycling stability when compared to pristine V3O7. A superior electrochemical performance and ultra-long cyclic stability of 94% over 2500 cycles was obtained through these developed electrodes.
We study the liquid mixture of sodium bis(trifluoromethanesulfonyl)imide in N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI-NaTFSI) for application in sodium-ion batteries. The ionic liquid-based electrolyte is characterized in terms of electrochemical and thermal properties. Ionic conductivity and electrochemical stability windows are evaluated through electrochemical impedance spectroscopy (EIS) measurements and voltammetry tests, respectively. The thermal stability is evaluated by differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Moreover, the suitability of the IL-electrolyte is preliminary verified in half and in full-cells at room temperature, using P2-Na0.6Ni0.22Fe0.11Mn0.66O2 layered oxide cathode and nanostructured Sb–C composite anode. The cell shows promising characteristics with a working voltage of about 2.7 V and a delivered capacity of about 100 mAh g−1. Despite requiring further optimization in terms of cycle life and energy density, the data here reported suggest the suitability of the ionic liquid electrolyte for application in sodium-ion battery.
Uniform and monodispersed TiO2 hollow spheres with nanoporous titania shell are prepared successfully by using carboxyl-functionalized polystyrene spheres as templates. The results show that TiO2 hollow spheres pose a stable reversible capacity of 230 mAhg−1 at 33.5 mAg−1 and 120 mAhg−1 at 1675 mAg−1, which are higher than that of bulk TiO2 with coarse grain. The discharge process of TiO2 hollow spheres are suggested containing three consecutive stages: the formation of tetragonal Li x TiO2 solid solution, coexistence of two-phase mixture of Li0.05TiO2 and Li0.5TiO2 at 1.75 V and additional lithium storage in the surface. The superior high rate and high capacity performance of prepared TiO2 hollow spheres are due to its highly reversible additional surface capacities and accommodation of phase transformation within nanostructure.
The acceptability, energy consumption, and environmental benefits of electric vehicles are highly dependent on travel patterns. With increasing ride-hailing popularity in mega-cities, urban mobility patterns are greatly changing; therefore, an investigation of the extent to which electric vehicles would satisfy the needs of ride-hailing drivers becomes important to support sustainable urban growth. A first step in this direction is reported here. GPS-trajectories of 144,867 drivers over 104 million km in Beijing were used to quantify the potential acceptability, energy consumption, and costs of ride-hailing electric vehicle fleets. Average daily travel distance and travel time for ride-hailing drivers was determined to be 129.4 km and 5.7 h; these values are substantially larger than those for household drivers (40.0 km and 1.5 h). Assuming slow level-1 (1.8 KW) or moderate level-2 (7.2 KW) charging is available at all home parking locations, battery electric vehicles with 200 km all electric range (BEV200) could be used by up to 47% or 78% of ride-hailing drivers and electrify up to 20% or 55% of total distance driven by the ride-hailing fleet. With level-2 charging available at home, work, and public parking, the acceptance ceiling increases to up to 91% of drivers and 80% of distance. Our study suggests that long range BEVs and widespread level-2 charging infrastructure are needed for large-scale electrification of ride-hailing mobility in Beijing. The marginal benefits of increased all electric range, effects on charging infrastructure distribution, and payback times are also presented and discussed. Given the observed heterogeneity of ride-hailing vehicle travel, our study outlines the importance of individual-level analysis to understand the electrification potential and future benefits of electric vehicles in the era of shared smart transportation.
Rechargeable sodium-ion batteries with aqueous electrolytes (aqueous SIBs) are highly desirable as low cost technologies for effective storage of intermittent sustainable energies because of their low cost and high safety. Polyanionic NaTi2(PO4)3 compound is particularly regarded as a promising anode material for aqueous SIBs, but suffering from low reaction kinetics and insufficient cycling stability in aqueous electrolytes. Herein, a carbon-encapsulated NaTi2(PO4)3 framework is fabricated as a high performance material for aqueous SIBs. Based on investigations of X-ray diffraction technique, elemental analysis and electrochemical measurements, it is found that the carbon encapsulation plays an important role in enhancing reaction kinetics of the material and suppressing dissolution of active NaTi2(PO4)3 component in aqueous electrolytes, therefore leading to improved structural stability and electrochemical reversibility. As a result, the material exhibits an impressive high-rate capability with a reversible capacity of 84mAhg−1 at 1000mAg−1, and ultra-long cycling lifetime with 96% capacity retention after 1000cycles. The finding in this study suggests that designing functional carbon-encapsulation structure can progress the NaTi2(PO4)3 anode material for long-lifespan aqueous SIBs.
Imperceptibility, robustness, and payload are three main requirements of any audio watermarking systems to guarantee desired functionalities, but there is a tradeoff among them from the information-theoretic perspective. Generally, in order to enhance the imperceptibility, robustness, and payload simultaneously, the human auditory system and the statistical properties of the audio signal should be fully taken into account. The statistical model based transform domain multiplicative watermarking scheme embodies the above ideas, and therefore the detection and extraction of the multiplicative watermarks have received a great deal of attention. Although much effort has been made in recent years, improving the ability of imperceptibility, watermark capacity, and robustness at the same time remains a challenge within the audio watermarking community. In this paper, we propose a blind audio watermark decoder in stationary wavelet transform domain based on bivariate generalized Gaussian distributions, wherein both the local statistical properties and inter-scale dependencies of the stationary wavelet transform coefficients of digital audio are taken into account, and also the adaptive nonlinear watermark embedding strength functions are designed. The results of our tests with different host audios, digital watermarks, and various attacks, we experimentally confirm that the proposed approach performs well compared to the state-of-the-art audio watermarking methods.
A manganese dioxide (MnO2) cathode with zinc (Zn) as the anode has been investigated using lithium sulphate (Li2SO4) as an electrolyte. Previously we demonstrated that cells comprising MnO2 and lithium hydroxide (LiOH) as an electrolyte can be made rechargeable to over one-electron capacity with a discharge capacity of 150 mAh g−1. Here we have extended our work to assess Li2SO4 as an electrolyte and have found that the battery is not rechargeable. Based on the electrochemical (discharge/charge) performance and the products formed following discharge and charge, the mechanism proposed for the sulphate-based media is one of proton insertion into the MnO2 cathode, rather than the lithium ion insertion observed for the LiOH electrolyte. The addition of bismuth species to the Li2SO4-based cell results in a transition to rechargeable behaviour. This is believed to be due to the influence of Bi ions on the formation of soluble Mn3+ soluble intermediates. However, the coulombic efficiency of the cell diminishes rapidly with repeated charge/discharge cycles. This confirms that the nature of the Li-containing electrolyte has a marked influence on the electrochemistry of the cell.
Li x Mn2O4 (LMO) and Li x Mn2O4–0.5ZrO2 (LMZO) thin films have been fabricated by radio-frequency (rf) sputtering deposition combined with conventional annealing method. The structures and surface morphology of thin films are characterized by X-ray diffraction, transmission electron microscopy, selected area electron diffraction and scanning electron microscopy techniques. It is shown that the addition of mass quantity of ZrO2 in LMZO can control the grain growth of nano-crystalline LMO. The electrochemical performances of all-solid-state thin film lithium batteries (TFBs) based on these thin films as cathodes are examined by cyclic voltammetry (CV), galvanostatic mode and alternate-current impedance measurements. Our results demonstrated that the addition of electrochemically inactive ZrO2 could significantly overcome the disadvantage of two distinct plateaus in 3 and 4V regions. LMZO is expected to become a promising cathode material for future TFBs.
A review on the preparation of the activated carbon from agricultural waste material is presented. The physical properties such as proximate and ultimate analysis of agricultural waste material were reviewed. The chemical compositions such as cellulose, hemicelluloses and lignin contents were also discussed. The effects of various parameters on the preparation such as carbonization and activation temperature, time, types of activating agents and impregnation ratio were reviewed. Various physical and chemical processes for the activation of the agricultural residues and their effects on the textural properties such as surface area and pore volume were discussed. The low cost, renewable and relatively less expensive of the agricultural waste were found to be efficiently being converted into wealth. The uses of activated carbon derived from agricultural residues in many fields were evidently proven in the review. The reaction kinetic modeling on the pyrolysis and activation of agricultural wastes were also reviewed.
Perinatal HIV infection negatively impacts cognitive functioning of children, main domains affected are working memory, processing speed and executive function. Early ART, even when interrupted, improves neurodevelopmental outcomes. Diffusion tension imaging (DTI) is a sensitive tool assessing white matter damage. We hypothesised that white matter measures in regions showing HIV-related alterations will be associated with lower neurodevelopmental scores in specific domains related to the functionality of the affected tracts.
The high cost of landfilling and the potential uses of waste foundry sands have prompted research into their beneficial reuse. Roadways have a high potential for large volume usage of the foundry sands. A laboratory testing program was conducted on soil-foundry sand mixtures amended with cement and lime to assess their applicability as highway subbase materials. The mixtures were compacted in the laboratory at a variety of moisture contents and compactive efforts and subjected to unconfined compression, California bearing ratio, and hydraulic conductivity tests. The environmental suitability of the prepared mixtures was evaluated by analyzing the effluent collected during hydraulic conductivity tests. Finally, required subbase thicknesses were calculated using the laboratory-based strength parameters. The results of the study show that the strength of a mixture is highly dependent on the curing period, compactive energy, lime or cement presence, and water content at compaction. The resistance of foundry sand-based specimens to winter conditions is generally better than that of a typical subbase reference material. Laboratory leaching tests indicated that if these mixtures later come in contact with water that has been discharged directly to the environment (e.g., drainage through asphalt pavement), the quality of water will not be affected.
In this contribution composite membranes have been prepared from acid–base polymer blend and solid inorganic proton conductive boron phosphate (BPO4). The blends are composed of sulfonated polyether-ether ketone (SPEEK) as the acidic component and polybenzimidazole (PBI) as the basic component. The contents of solid BPO4 in the composite membrane varied from 10 to 40wt%. The conductivity of the composite membranes was measured by impedance spectroscopy at room temperature. The conductivity of the composite membranes was found to increase with the incorporation of boron phosphate particles into blend membranes. The highest conductivity of 6mS/cm was found for composite membrane at room temperature. The membranes were characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and FTIR which showed acid–base interaction in the blend membranes and also confirmed the presence of solid BPO4 into the composite membranes. These membranes show good perspective in the membrane fuel cell applications.
Energy storage is often seen as necessary for the electric utility systems with large amounts of solar or wind power generation to compensate for the inability to schedule these facilities to match power demand. This study looks at the potential to use building thermal energy storage as a load shifting technology rather than traditional electric energy storage. Analyses are conducted using hourly electric load, temperature, wind speed, and solar radiation data for a 5-state central U.S. region in conjunction with simple computer simulations and economic models to evaluate the economic benefit of distributed building thermal energy storage (TES). The value of the TES is investigated as wind and solar power generation penetration increases. In addition, building side and smart grid enabled utility side storage management strategies are explored and compared. For a relative point of comparison, batteries are simulated and compared to TES. It is found that cooling TES value remains approximately constant as wind penetration increases, but generally decreases with increasing solar penetration. It is also clearly shown that the storage management strategy is vitally important to the economic value of TES; utility side operating methods perform with at least 75% greater value as compared to building side management strategies. In addition, TES compares fairly well against batteries, obtaining nearly 90% of the battery value in the base case; this result is significant considering TES can only impact building thermal loads, whereas batteries can impact any electrical load. Surprisingly, the value of energy storage does not increase substantially with increased wind and solar penetration and in some cases it decreases. This result is true for both TES and batteries and suggests that the tie between load shifting energy storage and renewable electric power generation may not be nearly as strong as typically thought.
The electrochemical properties of LiNi0.8Co0.2O2 coated with ZrO2 by three different coating processes (ball-milling, sol–gel method, simple grinding) were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). Results showed that the ZrO2 coating significantly improved the capacity retention of the cathode by suppressing the impedance growth at the interface between electrodes and electrolyte and the best cyclability was obtained in the case of employing the simple grinding for the ZrO2 coating. On the other hand, the initial capacities of the ZrO2-coated LiNi0.8Co0.2O2 cathode were slightly decreased.
Herein, we describe a case of an infertile man detected in postnatal diagnosis with FISH characterization and array-CGH used for genome-wide screening which allowed the identification of a complex rearrangement involving sex chromosomes, apparently without severe phenotypic consequences. The deletion detected in our patient has been compared with previously reported cases leading us to propose a hypothetical diagnostic algorithm that would be useful in similar clinical situations, with imperative multi disciplinary approach integrated with genetic counseling. Our patient, uniquely of reproductive age, is one of six reported cases of duplication of Xp22.3 (~8.4Mb) segment and contemporary deletion of Yq (~42.9Mb) with final karyotype as follows: 46,X,der(Y),t(X;Y)(Ypter→Yq11.221::Xp22.33→Xpter).ish der(Y) (Yptel+,Ycen+,RP11-529I21+,RP11-506M9-Yqtel−,Xptel+). arrXp22.33p22.31(702–8,395,963, 8,408,289x1), Yq11.221q12 (14,569,317x1, 14,587,321–57,440,839x0)
This paper conceptualizes and discusses the physical existence of electrically active dipoles in polymer-ceramic composite electrolytes. The concept of physical existence of dipoles is supported by experimental evidences that include time dependence, dc field assisted variation, and mechanically induced effects on conductivity.
The electrochemical reduction of oxidation products of tetrafluoro-p-hydroquinone, TFQH2, and 3-fluorocatechol, 3FQH2, in a 1.0M sulfuric acid solution is used as the positive electrode reaction to manufacture of hybrid redox flow batteries, HRFBs. Our previous studies and the results of this manuscript demonstrate that the electrochemical oxidation products 3FQH2 and TFQH2 are stable at time window of the cyclic voltammetric method as well as under different applied experimental conditions. Also, TFQH2 is a suitable compound for manufacturing of HRFBs. This is due to the stability of the electrochemical oxidation product of TFQH2 at time window of the electrolysis process. In addition, oxidation of electrodeposited cadmium on the copper electrode surface is used as the negative electrode reaction. Galvanostatic charge-discharge cycles are performed to determine the energy and coulombic performances of these compounds when they are used as active materials in fabrication of HRFBs. The proposed HRFBs were frequently charged and discharged in a voltage range of 0.8 to 1.6V. The results demonstrate stable charge-discharge cycling over 40cycles with the energy efficiency of 80% and a negligible capacity loss at room temperature for TFQH2. According to the experimental results, although the difference between the formal redox potential of 3FQH2 and cadmium is greater than that of TFQH2 and cadmium, the coulombic and energy efficiencies of an HRFB including TFQH2 is significantly higher than those of one including 3FQH2. Finally, TFQH2 is proposed as an excellent electroactive material for fabrication of an HRFB.