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We have investigated the structure and physical properties of Li-ion conducting polymer gel electrolytes functionalized with ionic liquid/lithium salt mixtures. The membranes are based on poly(vinylidene fluoride-co-hexafluoropropylene) copolymer, PVdF-HFP, and two ionic liquids: pyrrolidinium cations, N-butyl-N-methylpyrrolidinium (PyR14 +), N-butyl-N-ethylpyrrolidinium (PyR24 +), and bis(trifluoromethanesulfonyl)imide anion (TFSI). The ionic liquids where doped with 0.2 mol kg−-1 LiTFSI. The resulting membranes are freestanding, flexible, and nonvolatile. The structure of the polymer and the interactions between the polymer and the ionic liquid electrolyte have been studied using Raman spectroscopy. The ionic conductivity of the membranes has been studied using dielectric spectroscopy whereas the thermal properties were investigated using differential scanning caloriometry (DSC). These results show that there is a weak, but noticeable, influence on the physical properties of the ionic liquid by the confinement in the membrane. We observe a change in the Li-ion coordination, conformation of the anion, the fragility and a slight increase of the glass transition temperatures for IL/LiTFSI mixtures in the membranes compared to the neat mixtures. The effect can be related to the confinement of the liquid in the membrane and/or to interactions with the PVdF-HFP polymer matrix where the crystallinity is decreased compared to the starting polymer powder.
Composite membranes based on blends of sulfonated fluorinated poly(arylene ether) (SFPAE) and poly(vinylidene fluoride-co-hexafluoropropene) (P(VDF-co-HFP)) were prepared with varying P(VDF-co-HFP) content for vanadium redox flow battery (VRFB) applications. The properties of the SFPAE-P(VDF-co-HFP) blends were characterized by atomic force microscopy, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The water uptake, mechanical properties, thermal properties, proton conductivity, VO2+ permeability and VRFB cell performance of the composite membranes were investigated in detail and compared to the pristine SFPAE membrane. It was found that SFPAE had good compatibility with P(VDF-co-HFP) and the incorporation of P(VDF-co-HFP) increased the mechanical properties, thermal properties, and proton selectivity of the materials effectively. An SFPAE composite membrane with 10 wt.% P(VDF-co-HFP) exhibited a 44% increase in VRFB cell lifetime as compared to a cell with a pure SFPAE membrane. Therefore, the P(VDF-co-HFP) blending approach is a facile method for producing low-cost, high-performance VRFB membranes.
In order to increase the tap density of Li-rich layered materials, a new pre-heat treatment procedure of (Ni1/6Co1/6Mn4/6)CO3 precursors firstly using N2 and then O2 is adopted to separate processes of CO2 emission and O2 absorption, which presumably can reduce porosity of materials and then result in an improved tap density. In contrast to one-step pre-heat treatment procedure only in O2, two-steps procedure causes differences in morphology, tap density, particle distribution as well as structure for resultant metal oxides. A remarkably improved tap density of metal oxide with dense particles is observed with two-steps procedure. Consequently, Li1.167(Ni0.139Co0.139Mn0.556)O2 obtained through two-steps procedure (LM-N) presents dense particle, much improved tap density, small BET specific surface area and additional existence of Ni3+ in comparison with that obtained through one-step procedure (LM-O), although both samples exhibit similar well-defined layered structure. However, the results of cyclic voltammograms and charge–discharge test demonstrate the inferior electrochemical performances of LM-N with a discharge capacity of 76.7 mAh g−1 for LM-N, which is in stark contrast with 267.9 mAh g−1 of LM-O. This is possibly associated with the dense morphology, lattice defect as well as large Rct for LM-N.
Electrodes modified by polythiophenes bearing different substituents have been prepared and the behaviour of the conducting polymers has been studied with respect to the structural phenomena occurring in the correspondence to the doping and the relevant undoping processes. The effects of experimental parameters, such as undoping potential and time, have been investigated. The steric hindrance of the substituents on the polymer chain is demonstrated to play a fundamental role in determining the extent of compactness of the film, as induced by polarisation of the electrode at potentials at which the previously charged polymer is neutralised. Such a conclusion is in accordance with prediction of the electrochemical stimulated conformational relaxation model. Electrochemical AFM measurements have been performed in order to acquire a direct view of the morphological modifications of the polymer coatings during the reduction.
A novel solvoplasma based technique was used to fabricate highly uniform SnO2 nanowires (NWs) for application as an anode in sodium-ion batteries (SIBs). This technique is scalable, rapid, and utilizes a rigorous cleaning process to produce very pure SnO2 NWs with enhanced porosity; which improves sodium-ion hosting and reaction kinetics. The batch of NWs obtained from the plasma process were named the “as-made” sample and after cleaning the “pure” sample. Structural characterization showed that the as-made sample has a K+ ion impurity which is absent in the pure samples. The pure samples have a higher maximum specific capacity, 400.71 mAhg−1, and Coulombic efficiency, 85%, compared to the as-made samples which have a maximum specific capacity of 174.69 mAhg−1 and Coulombic efficiency of 74% upon cycling. A study of the electrochemical impedance spectra showed that the as-made samples have a higher interfacial and diffusion resistance than the pure samples and resistances increased after 50 cycles of cell operation for both samples due to progressive electrode degradation. Specific energy vs specific power plots were employed to analyze the performance of the system with respect to the working conditions.
Recently haptic shape modeling has got a momentum in industrial and conceptual design. In this paper, a real-time haptic interface of synthesized shape modeling and haptic function evaluation of product design for multi-material part is presented. Due to the advancement of manufacturing technologies, multi-material is increasingly employed by industrial designers as a means for increasing the appeals of a product while also adding functional capability. Multi-material part manufacturing processes allow designers to select different materials for different portions of a product in order to improve the material-function compatibility for the overall product. For quick design verification, the shape design and function evaluation are implemented in the same haptic environment where a load can be applied to a part design using a haptic device and at the same time the combined reaction of the part in terms of displacement and reaction can be visualized and felt by the user. The intuitive correlation between the applied force and incurred displacement (or deflection) provides an instant evaluation of the stiffness of a part design. The proposed methodology is illustrated through a case study: the design of a toothbrush.
We report electrochemical studies of high voltage cathodes composed of lithium rich “layered-layered” material having the nominal composition Li1.2Mn0.525Ni0.175Co0.1O2, or equivalently 0.6Li[Li1/3Mn2/3]O2–0.4Li[Mn0.3Ni0.45Co0.25]O2. These aspects were investigated by cyclic voltammetry studies in conjunction with electrochemical impedance spectroscopy measurements to understand the redox reactions involving multiple transition metals and their capacity contribution at higher voltages, up to 4.9V. Further, cathodes with 1.5wt.% carbon nanofibers added to the Li1.2Mn0.525Ni0.175Co0.1O2 composite electrode showed stable reversible capacities of about 280mAhg−1 when cycled to 4.9V for more than 100 cycles, and almost a factor of two improvements in the rate performance compared to the electrode composition prepared using conventional composition (7.5% carbon black and 7.5% binder).
This research was carried out to prepare high performance membrane electrode assemblies (MEAs) for a proton exchange membrane fuel cell (PEMFC). The MEAs were prepared by introducing a microporous sublayer (MPS) between the gas diffusion layer and the catalyst layer. Main parameters for MPS preparation, which are microporous carbon types and the polytetrafluoroethylene (PTFE) content in the MPS, were investigated. Three microporous carbon types, which are Hicon Black, RGN and Vulcan, were evaluated. Then, Nafion membranes with two thicknesses were employed to form an MEA. The preliminary results demonstrated that a high performance could be achieved with the presence of Hicon Black in the MPS and the performance was comparable to those with the presence of Vulcan XC-72, particularly in the high current density region. The optimum PTFE content was found to be 6 wt% and the thinner membrane provided a better cell performance. The highest current density was 858 mA cm−2 at the cell potential of 0.6 V.
Although Li–O2 batteries can potentially achieve greater than two-fold higher energy densities than Li-ion batteries, the basic performance of Li–O2 batteries remains poor. In particular, the large over-potential of positive electrode reactions during the charging process results in low round-trip energy efficiency and limited cycle life, and is therefore the main barrier to the practical use of rechargeable Li–O2 batteries. In the present study, we demonstrate that the charging performance of Li–O2 batteries can be significantly improved by simply adding barium (Ba) ions into the electrolyte. Elemental analysis revealed that Ba-incorporated Li2O2 was obtained as the main discharge product of a Li–O2 cell operated in the presence of Ba2+. Notably, the improvement of charging performance was confirmed to originate from the Ba-incorporated Li2O2 deposits, rather than the Ba2+ present in the electrolyte. The present results suggest that the incorporation of heteroatoms into the discharge product is an effective approach for improving the charging performance of Li–O2 batteries.
Energy storage capacity has been a major limiting factor in pursuit of increasing functionality and mobility for portable devices. To increase capacity limits, novel battery designs with multi-electron redox couples and increased voltages have been listed as a priority research direction by the US Department of Energy. This study leverages the benefits of microfluidics technology to develop a novel mixed-pH media aluminum–air cell which incorporates the advantages of the trivalence of aluminum and mixed-pH thermodynamics. Experimentally, the new cell exhibited an open circuit potential of 2.2V and a maximum power density of 176mWcm−2, which are respectively 37.5% and 104.6% higher than conventional single alkaline aluminum–air cell under similar conditions. With further optimization of channel thickness, a power density of 216mWcm−2 was achieved in the present study.
Samples of a SnCoC-based electrodes, all having the molar composition Sn40Co40C20, but differing by the high energy ball milling synthesis conditions, have been tested in lithium cells. The investigation was carried out by using a series of complementary techniques, including potentiodynamic cycling with galvanostatic acceleration, galvanostatic charge–discharge cycling and impedance spectroscopy. The results confirmed the high capacity delivery of this type of ternary electrodes but also revealed that their electrochemical behaviour is influenced by the relative abundance of the nanosized domains of CoSn and CoSn2 in their structure.
Sustainable alkaline metal ion batteries using organic electrodes are promising for large-scale renewable energy storage. Traditional anode compounds are always anchored with harmful aromatic rings, which results in high toxicity. In this work, a series of aromatics-free organic electrode material based on an azo group is applied in alkaline metal ion batteries. Lithium-, sodium- and potassium-ion batteries based on acyclic compound 2, 2′-azobis(2-methylpropionitrile) (AIBN) as an anode material exhibit low toxicity. In situ Raman and ex situ Fourier-transform infrared spectroscopy results reveal that the azo group serves as the electrochemical active site for the reversible insertion and extraction of alkaline metal ions. Another compound with low toxic, 2,2′-azobis(2-methylpropionamidine) dihydrochloride (AIBA), which containing two active sites of azo and imine groups confirmed with in situ Raman and ex situ FT-IR, are applied in lithium-ion batteries. Furthermore, harmless sodium ion battery has been assembled with azodicarbonamide (CONH). Therefore, this acyclic compound offers possibilities in novel organic electrode materials for developing toxin-free and environmental-friendly alkaline metal ion batteries.
Health issues related to aquifer contamination with perchlorate are a growing concern in drinking water management. This study describes perchlorate transport and degradation processes from a contaminated stream toward drinking water pumping wells. Investigations are based on laboratory experiments and field measurements conducted at a well field near Bordeaux (France) in a heterogeneous carbonate aquifer interacting with a stream. Field measurements facilitated the characterization of perchlorate contamination and stream-to-aquifer flow. Experiments on columns of streambed sediments conducted in the laboratory confirmed that perchlorate had been degraded in the hyporheic zone. A one-dimensional reactive transport model was implemented to estimate Monod kinetic rates, which account for the inhibition of perchlorate degradation by nitrate. The estimated half-saturation constant for perchlorate
Background Memory profiles corresponding to nearly normal (NN), Subcortical impairment (Sub) and Cortical impairment (Cort) have been identified in schizophrenia by several investigators using cluster analytic techniques. Specific aims of the current study were to (1) perform a K means cluster analysis using Hopkins Verbal Learning Test-R scores (2) create classification rules based upon cluster distributions and expected memory profiles and to determine their concordance with cluster analysis; (3) explore differences among classified groups on demographic, neurocognitive and social cognitive domains; and (4) determine the stability of the classifications 12months later. Methods Clinical and neuropsychological assessments were obtained at intake and 12months from 151 outpatients with schizophrenia or schizoaffective disorder from an urban community mental health center. Results Clusters corresponded to those of the three expected subgroups. Using simple decision rules, rationally-derived groups were created and had 90% classification agreement with cluster groups. Groups did not differ on illness characteristics. Groups differed significantly in neurocognitive and social cognitive domains with NN>Cort and NN>Sub in all domains except visual/motor speed. Sub>Cort in verbal working memory. NN>Cort in social cognition. Rationally derived groupings showed fair stability at 12month follow-up with 65% classification agreement. Specificity was good for NN (82.4%). Discussion Results support validity of memory profiles and offer some support for their stability at 12months. The simple rules for classification can be used by other investigators for neuroimaging and other studies. Findings support the hypothesis that verbal memory may be an important source of heterogeneity in schizophrenia.
Chemokine receptor 5 (CCR5) is an important receptor used by human immunodeficiency virus type 1 (HIV-1) to gain viral entry into host cell. In this study, we used a combined approach of comparative modeling, molecular docking, and three dimensional quantitative structure activity relationship (3D-QSAR) analyses to elucidate detailed interaction of CCR5 with their inhibitors. Docking study of the most potent inhibitor from a series of compounds was done to derive the bioactive conformation. Parameters such as random selection, rational selection, different charges and grid spacing were utilized in the model development to check their performance on the model predictivity. Final comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) models were chosen based on the rational selection method, Gasteiger-Hückel charges and a grid spacing of 0.5 Å. Rational model for CoMFA (q2 = 0.722, r2 = 0.884, Q2 = 0.669) and CoMSIA (q2 = 0.712, r2 = 0.825, Q2 = 0.522) was obtained with good statistics. Mapping of contour maps onto CCR5 interface led us to better understand of the ligand–protein interaction. Docking analysis revealed that the Glu283 is crucial for interaction. Two new amino acid residues, Tyr89 and Thr167 were identified as important in ligand–protein interaction. No site directed mutagenesis studies on these residues have been reported.
This paper presents results from positive matrix factorization (PMF) of organic molecular marker data to investigate the sources of organic carbon (OC) in Pittsburgh, Pennsylvania. PMF analysis of 21 different combinations of input species found essentially the same seven factors with distinctive source-class-specific groupings of molecular markers. To link factors with source classes we directly compare PMF factor profiles with actual source profiles. Six of the PMF factors appear related to primary emissions from sources such as motor vehicles, biomass combustion, and food cooking. Each primary factor contributed between 5% and 10% of the annual-average OC with the exception of the cooking related factor which contributed 20% of the OC. However, the contribution of the cooking factor was sensitive to the specific combinations of input species. PMF could not differentiate between gasoline and diesel emissions, but the aggregate contribution of primary emissions from these two source classes is estimated to be less than 10% of the annual-average OC. One factor appears related to secondary organic aerosol based on its substantial contribution to biogenic oxidation products. This secondary factor contributed more than 50% of the summertime average OC. Reasonable agreement was observed between the PMF results and those of a previously published chemical mass balance (CMB) analysis of the same molecular marker dataset. Individual PMF factors are correlated with specific CMB sources, but systematic biases exist between the two estimates. These biases were generally within the uncertainty of the two estimates, but there is also evidence that PMF is not cleanly differentiating between source classes.
This paper proposes an optimal control strategy for a standalone PV system with Battery-Supercapacitor Hybrid Energy Storage System to prolong battery lifespan by reducing the dynamic stress and peak current demand of the battery. Unlike the conventional methods which only use either filtration based controller (FBC) or fuzzy logic controller (FLC), the proposed control strategy comprises of a low-pass filter (LPF) and FLC. Firstly, LPF removes the high dynamic components from the battery demand. FLC minimizes the battery peak current demand while constantly considering the state-of-charge of the supercapacitor. Particle swarm optimization (PSO) algorithm optimizes the membership functions of the FLC to achieve optimal battery peak current reduction. The proposed system is compared to the conventional system with battery-only storage and the systems with conventional control strategies (Rule Based Controller and FBC). The proposed system reduces the battery peak current, battery peak power, maximum absolute value of the rate of change of power and average absolute value of the rate of change of power by 16.05%, 15.19%, 77.01%, and 95.59%, respectively as compared to the conventional system with battery-only storage. Moreover, he proposed system increases the level of supercapacitor utilization up to 687.122% in comparison to the conventional control strategies.
Present paper reports the survey on existing research literatures in connection with various energy management issues/benefits of a microgrid arising due to strategic deployment of its DERs. Survey on regulatory issues includes various barriers, incentives, standards (IEEE 1547, UL-1741, etc.), environmental issues, ancillary services and metering. Economic benefits, like improvement of bus voltages, line loss reduction, deferral of upgrade, waste heat utilization, reduction of customer interruption cost (CIC), ancillary services, emission reduction, fuel cost minimization, etc. have been surveyed from many researchers’ literatures in relation to methods of analyses, algorithms used and their quantification. A brief survey of researchers’ opinion on DER technologies in their respective economic analysis has also been included. This paper also reviews the researches and studies on tariff structure, market strategy of microgrid energy (both electric and thermal).
The prevalence of Salmonella in seafood samples collected from the southwest coast of India was studied by conventional culture and by a DNA based molecular technique, polymerase chain reaction (PCR). While conventional culture techniques detected Salmonella in only 20 out of the 100 samples analyzed, direct enrichment lysate PCR detected 52 as positive for Salmonella. A set of three different PCR primers viz., hns, invA and invE were used. It was observed that hns primer detected Salmonella in a significantly higher number of samples. Fourteen out of nineteen isolates belonged to serovar S. enterica Weltevreden. S. Weltevreden isolates were genotyped yielding 4 different patterns both by RAPD and ERIC-PCR but when combined, the overall results discriminated the isolates of S. Weltevreden into 6 different types. This suggests that genetically diverse Salmonella Weltevreden are prevalent in seafood.
Few studies have investigated predictors of response to cognitive remediation interventions in patients with schizophrenia. Predictor studies to date have selected treatment outcome measures that were either part of the remediation intervention itself or closely linked to the intervention with few studies investigating factors that predict generalization to measures of everyday life-skills as an index of treatment-related improvement. In the current study we investigated the relationship between four measures of neurocognitive function, crystallized verbal ability, auditory sustained attention and working memory, verbal learning and memory, and problem-solving, two measures of symptoms, total positive and negative symptoms, and the process variables of treatment intensity and duration, to change on a performance-based measure of everyday life-skills after a year of computer-assisted cognitive remediation offered as part of intensive outpatient rehabilitation treatment. Thirty-six patients with schizophrenia or schizoaffective disorder were studied. Results of a linear regression model revealed that auditory attention and working memory predicted a significant amount of the variance in change in performance-based measures of everyday life skills after cognitive remediation, even when variance for all other neurocognitive variables in the model was controlled. Stepwise regression revealed that auditory attention and working memory predicted change in everyday life-skills across the trial even when baseline life-skill scores, symptoms and treatment process variables were controlled. These findings emphasize the importance of sustained auditory attention and working memory for benefiting from extended programs of cognitive remediation.