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Rechargeable zinc-air batteries are attracting enormous attention owing to their extremely high specific energy densities. However, their large scale deployment hinges on the discovery of cheap and efficient electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). Herein, the successful synthesis of a bifunctional hybrid electrocatalyst capable of driving both OER and ORR is reported, comprising Co,N-codoped carbon nanoframes (Co,N-CNF) decorated with 14nm Ni3FeN particles, in which the Co,N-codoped carbon nanoframe (Co,N-CNF) with ORR activity was introduced as a scaffold to disperse the precursors and mitigate their further aggregation. The Ni3FeN/Co,N-CNF hybrid afforded remarkable OER activity (overpotential of 0.27V, superior to IrO2) and excellent ORR performance (half-wave potential of 0.81V vs RHE, superior to Pt/C), the origins of which can be traced to the inherent activities of the metallic Ni3FeN nanoparticles and Co,N-CNF support, respectively. Cathodes made from the Ni3FeN/Co,N-CNF electrocatalyst demonstrated superior efficiency and durability to state-of-the-art Pt/C+IrO2 electrocatalysts in both primary and rechargeable zinc-air batteries, showcasing the versatility of the newly developed Ni3FeN/Co,N-CNF electrocatalyst system.
Polypyrrole@Sulfur@Polypyrrole composite with a novel three-layer-3D-structure, which consists of an external polypyrrole coating layer, an intermediate sulfur filling layer, and an internal polypyrrole split-half-tube conducting matrix layer, has been synthesized by the oxidative chemical polymerization method and chemical precipitation method in this article. Due to this unique three-layer-structure, the discharge specific capacity of Polypyrrole@Sulfur@Polypyrrole composite cathode retained at 554mAh g−1 after 50 cycles, which represents 68.8% retention of the initial discharge specific capacity. In comparison, the Sulfur@Polypyrrole composite cathode, with the same components as Polypyrrole@Sulfur@Polypyrrole composite, but without the three-layer-structure, has the discharge specific capacity of 370mAh g−1 after 50 cycles, which is 32.3% retention of the initial discharge specific capacity. Therefore, it can be concluded that the unique three-layer-structure plays an essential role in improving the performance of the Lithium/Sulfur batteries. Moreover, the effects of LiNO3 additive in the electrolyte on coulombic efficiency are discussed to further confirm the containment function of the external layer of polypyrrole in the Polypyrrole@Sulfur@Polypyrrole composite, which is the evidence that the external layer of polypyrrole can effectively confine the dissolved polysulfides.
In this paper, Nano-sized hard carbon spherule (HCS) is prepared from the distilled water/ethylene glycol mixed solution by hydrothermal technique. Due to the addition of ethylene glycol, the as-prepared sample is a kind of nano-sized HCS and the particle size of nano-sized HCS is 50–100nm. Furthermore, nano-sized HCS displays larger specific surface area attributed to the well-dispersed property. As a result, it shows lower charge transfer impedance than that of micro-sized HCS owing to the huge contact area between particles and electrolyte. However, the initial coulombic efficiency of nano-sized HCS is a little lower than that of micro-sized HCS due to the large specific surface area for electrolyte irreversible decomposition. Charge-discharge cycling tests demonstrate that nano-sized HCS samples have high capacity retention ratio (92.7%) and high reversible lithium storage performance (525mAhg−1). Therefore, it is a potential anode material for lithium–ion batteries.
Small and detrimental, albeit inconsistent, effects of prenatal cocaine exposure (PCE) during early childhood have been reported. The teratogenic effects of prenatal alcohol (PAE) and tobacco exposure (PTE) on neurobehavior are more firmly established than PCE. We tested if co-exposure to all three drugs could be related to greater differences in brain structure than exposure to cocaine alone. Participants (n =42, PCE=27; age range=14–16 years) received an executive function battery prior to a T1-weighted 3T structural MRI scan. Cortical thickness was measured using FreeSurfer (v5.1). Fetal drug exposure was quantified through maternal self-reports usage during pregnancy. Using general linear modeling, we found no main effects of PCE on cortical thickness, but significant main effects of PAE and PTE in superior and medial frontal regions, after co-varying for the effects of age, sex, and each drug of exposure. Significant alcohol-by-tobacco interactions, and significant cocaine-by-alcohol interactions on cortical thickness in medial parietal and temporal regions were also observed. Poly-drug exposure and cognitive function also showed significant interactions with cortical thickness: lower cortical thickness was associated with better performance in PCE-exposed adolescents. Results suggest that although children with PCE have subtle but persistent brain cortical differences until mid-to-late adolescence.
Co-doped NiO nanoflake arrays with a cellular-like morphology are fabricated by low temperature chemical bath deposition. As anode material for lithium ion batteries (LIBs), the array film shows a capacity of 600mAhg−1 after 50 discharge/charge cycles at low current density of 100mAg−1, and it retains 471mAhg−1 when the current density is increased to 2Ag−1. Appropriate electrode configuration possesses some unique features, including high electrode–electrolyte contact area, direct contact between each naonflake and current collector, fast Li+ diffusion. The Co2+ partially substitutes Ni3+, resulting in an increase of holes concentration, and therefore improved p-type conductivity, which is useful to reduce charge transfer resistance during the charge/discharge process. The synergetic effect of these two parts can account for the improved electrochemical performance.
Single crystalline cubic spinel LiMn2O4 nanowires were synthesized by hydrothermal method and the precursor calcinations. The phase structures and morphologies were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and high-resolution transmission electron microscopy (HRTEM). Galvanostatic charging/discharging cycles of as-prepared LiMn2O4 nanowires were performed in an aqueous LiNO3 solution. The initial discharge capacity of LiMn2O4 nanowires was 110mAhg−1, and the discharge capacity was still above 100mAhg−1 after 56 cycles at 10C-rate, and then 72mAhg−1 was registered after 130 cycles. This is the first report of a successful use of single crystalline spinel LiMn2O4 nanowire as cathode material for the aqueous rechargeable lithium battery (ARLB).
We report on in situ and ex situ concentration measurements in lithium/polymer–electrolyte/lithium cells during cycling. We have used three different methods which give complementary results, in good agreement with theoretical predictions and previous concentration measurements by Raman confocal microspectroscopy. Our methods allow to obtain concentration maps in the electrolyte, in particular, when dendrites are observed: from these measurements, we can correlate the onset of dendritic growth with local concentration gradients.
Large number of rooftop Photovoltaics (PVs) have turned traditional passive networks into active networks with intermittent and bidirectional power flow. A community based distribution network grid reinforcement process is proposed to address technical challenges associated with large integration of rooftop PVs. Probabilistic estimation of intermittent PV generation is considered. Depending on the network parameters such as the R/X ratio of distribution feeder, either reactive control from PVs or coordinated control of PVs and Battery Energy Storage (BES) has been proposed. Determination of BES capacity is one of the significant outcomes from the proposed method and several factors such as variation in PV installed capacity as well as participation from community members are analyzed. The proposed approach is convenient for the community members providing them flexibility of managing their integrated PV and BES systems.
Unknown Note: Page numbers followed by “b” and “t” refer to boxes and tables, respectively.
In this investigation the environmental impacts of the manufacturing processes of a new all-solid-state battery (SSB) concept in a pouch bag housing were assessed using the Life Cycle Assessment (LCA) methodology for the first time. To do so, the different production steps were investigated in detail, based on actual laboratory scale production processes. All in- and outputs regarding material and energy flows were collected and assessed. As LCA investigations of products in an early state of research and development usually result in comparatively higher results than those of mature technologies in most impact categories, potential future improvements of production processes and efficiency were considered by adding two concepts to the investigation. Apart from the laboratory production which depicts the current workflow, an idealized laboratory production and a possible industrial production were portrayed as well. The results indicate that electricity consumption plays a big role due to a lot of high temperature production steps. It needs to be improved for future industrial production. Also enhanced battery performance can strongly influence the results. Overall the laboratory scale results indeed improve strongly when assuming a careful use of resources, which will likely be a predominant target for industrial production. These findings therefore highlight hotspots and give improvement targets for future developments. It can also be deducted, that a comparison to the results of competing technologies that have already reached a commercial stage is not recommended for early LCAs. To round things off a resource analysis was also conducted. It identifies the usage of lanthanum, lithium and zirconium oxide as critical, especially when taking laboratory production as a base. When looking at the scale up to industrial production parameters, lanthanum and lithium remain critical, zirconium oxide not.
Technology selection, which influences the competitive advantages of an enterprise or a country, is a multi-criteria decision issue. In addition, it is increasingly difficult to identify the right technologies because technologies are increasing in number and complexity. This study proposes a technology selection process integrating the fuzzy analytic hierarchy process (AHP) and Delphi method. The former effectively conducts the fuzziness existing in experts' responses and identifies the strength of technology selection criteria and the relationship between the two. The latter provides the main technology alternatives for Taiwan's future photovoltaic industry. Finally, through the two-way linkage between technology selection criteria and main industrial technologies, the technology fields of the photovoltaic industry can be identified. The empirical results indicate that the benefit of a technology is the most important factor among technological selection criteria, and that Taiwan should adopt and develop microcrystalline silicon film multi-junction and amorphous-silicon solar cells as its main industrial technologies. The results may serve to guide industrial technology acquisition and the work of resource allocations on the behalf of government and enterprises.
The rapid tidal current near a lake inlet is transformed into electrical energy with Darius-type hydraulic turbine generators. When the tidal power generation is insufficient, the stored excess electric power generated from midnight to early morning of a representative day is used. The balance of energy supply and demand for all sampling events in a representative day must be predicted very accurately in a system with energy storage. In this study, electric power and heat demand are forecasted on the basis of weather data obtained from the Internet, and the corresponding values are used to plan the storage of electricity and heat from midnight to early morning. The results of the case analysis show the influence of the economic efficiency of the heating system, the capacity of the tidal power generator, the prediction error of the tidal power generator, and the insulation efficiency (Q-value) on the energy cost. Optimization of the introduced simulation model was considered. The objective functions of optimization were minimization of operation cost and facilities cost of the simulation model.
A simple, one-pot route was developed for the synthesis of SnO2-reduced graphene oxide (RGO) composites. Simultaneous reduction of graphene oxide (GO) and heterogeneous nucleation and growth of SnO2 on the surface of RGO under the supercritical methanol medium resulted in uniform deposition of well-dispersed SnO2 nanoparticles on the RGO sheets. In comparison with the bare SnO2 nanoparticles and bare RGO sheets, the as-synthesized SnO2-RGO composites exhibited enhanced Li-ion storage and high rate performance. The SnO2-RGO composite with a SnO2 loading of 58 wt% delivered a reversible discharge capacity of 776 mAh g−1 after 70 cycles at a current density of 0.1 A g−1 and a rate performance of 147 mAh g−1 at a high current density of 5 A g−1. In addition, after 1000 continuous cycles at 1 A g−1, the composite electrode exhibited a reversible discharge capacity as high as 531 mAh g−1 with excellent capacity retention. The enhanced long-term cyclability and high-rate performance of the SnO2-RGO composite can be attributed to the effective confinement of SnO2 nanoparticles on the RGO sheets, and thus, the interparticle agglomeration and volume change associated with alloying–dealloying of SnO2 during cycling can be prevented and cell integrity can be maintained.
Orthorhombic LiMnO2 (o-LiMnO2) is known to have stacking faults (local regions of monoclinic ordering) that are caused by structure disorder between Li and Mn sites. Previous research has indicated that this structural disorder, correlated with the full width at half maximum (FWHM) of the (110) X-ray diffraction (XRD) peak, might affect the electrochemical properties of o-LiMnO2. In this study, o-LiMnO2 powders are prepared by an emulsion drying method. Different degrees of stacking faults are induced by varying the heating rate. From electrochemical and ex situ XRD experiments, it is found that a sample with a high number of stacking faults undergoes easier phase transformation from the orthorhombic to the spinel structure on cycling. This form of o-LiMnO2 displays no capacity fading in the 4V (versus Li/Li+) region, but suffers severe capacity fading in the 3-V region. By contrast, a sample with a low number of stacking faults experiences no capacity fading in either the 3- or 4-V regions and has good cycleability.
A prelithiated carbon anode has been produced incorporating stabilised lithium metal powder. Electrodes have been fabricated which are partially lithiated, to compensate for the irreversible capacity of the anode material and combined with conventional Li-ion cathode materials. Fully lithiated anodes have also been fabricated and combined with non-lithiated cathode materials to produce a Li-ion cell.
Our environment is in threat due to a variety of pollutants. One of the major causes of pollution is industrial wastewater leading to adverse effect on the existence of living organisms. In this scenario, certain metal and metal oxide nanoparticles have shown their ability as catalysts in degrading these organic pollutants. In the present study, tannic acid is used for the synthesis of nanostructured NiO and SnO2 which have the potential to act as nanocatalyst. As this synthesis technique does not involve any toxic chemicals, they are environmentally benign. The complexes formed are annealed at 873 K, as shown by TGA–DTG analysis, for 2 h to obtain pure NiO and SnO2 nanomaterials. The prepared nanomaterials are characterized using XRD, HRTEM, EDAX, UV–visible and FTIR spectra. The catalytic potential of both NiO and SnO2 are manifested by monitoring by the degradation of the heterocyclic aromatic dye methylene blue to leucomethylene blue using UV–visible spectrophotometer. The rate constant is found to be 0.0006 min−1 for the reaction unassisted by nano-catalyst. In the presence of nanostructured NiO and SnO2, the rate constants are 0.026 min−1 and 0.323 min−1, respectively, showing good catalytic potential for the synthesized nanomaterials.
Selecting an appropriate invertebrate assay has been a primary goal of national and international testing programs for endocrine disrupting chemicals. The available information on the endocrine system, its hormones and their modes of action in controlling physiological processes in invertebrates is limited and the selection of appropriate test species still presents a challenge. This paper outlines the development of a higher-tier full life cycle (FLC) test for pesticides with the non-biting midge Chironomus riparius (Insecta, Diptera, Chironomidae). As an insect, C. riparius represents the species’ richest and ecologically one of the most important groups of invertebrates. In addition, the endocrine system of insects is one of the best studied among the invertebrates. Acute and chronic tests with Chironomus spp. are commonly used for testing and risk assessment of agrochemicals. A chironomid FLC test protocol has been developed and its suitability investigated in an inter-laboratory comparison. The protocol used is based on existing OECD and US-EPA test methods. To verify the suitability of the test to generate endpoints that encompass adverse effects on the arthropod endocrine system, a juvenile hormone analog was selected as positive control substance. Results have demonstrated that the proposed chironomid FLC can be performed in separate laboratories and that the selected arthropod juvenile hormone mimic causes effects. However, the observed toxicity is not proof of an endocrine disruptive mechanism and could equally be evoked by other compounds. Contrary to a screening assay, which aims at revealing a substance’s mode-of-action, the FLC test generates robust, population-relevant endpoints that can be used in the risk assessment of agrochemicals. Since the initial results presented in this paper are encouraging we propose to complete the validation of this assay under OECD with high priority.
Current research trends on energy storage have given new impetus to the development of sodium-ion batteries. In this context, titanium phosphates with a NASICON-related structure are known to provide a stable crystal structure for sodium mobility. With adequate redox centers, these materials are studied here as attractive cathodes vs. sodium. Powdered solids of general stoichiometry Na1+x Ti2−x Fe x (PO4)3 (0 ≤ x ≤ 0.8) were obtained and electrochemically tested. The structural modifications induced by the substitution of Ti4+ by Fe3+ were analyzed by X-ray diffraction revealing an anisotropic change of the unit cell parameters. A continuous voltage decrease is observed between 2.6 and 2.0 V in the iron containing samples, which was ascribed to the contribution of the Fe3+/Fe2+ redox couple, as determined by 57Fe Mössbauer spectroscopy. A detailed analysis of this region revealed the occurrence of local orderings of inserted sodium ions. The introduction of low contents of iron (x = 0.2) involved a capacity value of 130.2 mA h g−1 after the first discharge and a good capacity retention after an extended cycling. It was correlated to the low internal resistance values for this composition.
Sn/WC/graphene (Sn/WC/G) triple layered composite in which Sn thin-layer (3–10nm) enwrapped in-between WC (tungsten carbide) substrate and few-layer graphene is prepared via a simple two-step ball-milling approach. The as prepared triple layered composite exhibits superior cyclability with high capacity and rate capability in lithium-ion half cells, i.e., ca. retains 91% of its initial capacity (400mAhg−1) after 100 cycles and delivers a high capacity of ∼200mAhg−1 at a very high rate of 8C (4000mAg−1). The improvement in the electrochemical performance can be attributed to the triple layered structure in which the inner WC and outer graphene conductive buffer matrix not only can buffer the volume changes of the Sn thin-layer during cycling, but also ensure good electrical contact of the electro-active particles. Furthermore, a full cell coupled with spinel LiNi0.5Mn1.5O4 cathode in this paper demonstrates full utilization of the Sn anode and an expected energy density value of 530Whkg−1, showing a prospect for practical lithium-ion battery applications.
This paper treats supercapacitors matrix characterization. In order to cut off transient power peaks and to compensate for the intrinsic limitations in embedded sources, the use of supercapacitors as a storage system is quite suitable, because of their appropriate electrical characteristics (huge capacitance, small series resistance, high specific energy, high specific power), direct storage (energy ready for use), and easy control by power electronic conversion. This use requires supercapacitors modules where several cells connected in serial and/or in parallel, thus a bypass system to balance the charging or the discharging of supercapacitors is required. In the matrix of supercapacitors, six elements of three parallel BCAP0350 supercapacitors in serial connections have been considered. This topology permits to reduce the number of the bypass circuits and it can work in degraded mode. Actually, it allows the system to have more reliability by providing power continually to the load even when there are one or more cells failed. Simulation and experimental results are presented and discussed.
This paper focuses on the mechanism and kinetics of the borohydride oxidation reaction (BOR). This reaction was studied by quasi-steady-state hydrodynamic cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) on a gold rotating disk electrode (RDE). The best operating conditions to obtain stable and reproducible experimental data were first surveyed: only (i) electrolyte solutions much more diluted than practical DBFC anolyte (e.g. 0.01M NaOH+5×10−5 M NaBH4) and (ii) polarization of the gold electrode strictly below the region of gold oxide formation, are compatible with quasi-steady-state measurements. Both this diluted solution and a more classical one (0.1M NaOH+10−3 M NaBH4) were eventually investigated, the latter for comparison purposes with relevant literature data. From the modeling of the CV and EIS experimental data and consecutive parametric identification, a simplified reaction pathway was proposed, the theoretical behavior of which agrees with the experimental findings. Whatever the composition of electrolyte used, this pathway includes at least two electrochemical steps (EE) for the BH4 − oxidation. Using the expression of the faradaic current density, concentration impedance and electrode impedance for the redox EE reaction, the theoretical steady-state hydrodynamic CV and EIS spectra can be calculated. The obtained simulated plots are representative to the corresponding experimental CV and EIS traces. However, the values of the kinetic parameters calculated from such modeling are weak, suggesting that the redox EE is still a simplification of the actual borohydride oxidation reaction pathway on gold in diluted sodium borohydride solutions.