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Recently, aluminum–air (Al–air) batteries have received attention from researchers as an exciting option for safe and efficient batteries. The electrochemical performance of Aluminum anode remains an active area of investigation. In this paper, the electrochemical properties of polycrystalline Al, Al (001), (110) and (111) single crystals are investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 4 M NaOH and KOH. Hydrogen corrosion rates of the Al anodes are determined by hydrogen collection. Battery performance using the anodes is tested by constant current discharge at 10 mA cm−2. This is the first report showing that the electrochemical properties of Al are closely related to the crystallographic orientation in alkaline electrolytes. The (001) crystallographic plane has good corrosion resistance but (110) is more sensitive. Al (001) single crystals display higher anode efficiency and capacity density. Controlling the crystallographic orientation of the Al anode is another way to improve the performance of Al–air batteries in alkaline electrolytes.
Pb–Sn alloys of 0–2.0 mass% Sn and Pb–2mass% Sn–Sr alloys of 0–0.50 mass% Sr were evaluated by the corrosion test with repetitive current application. The mass change of the specimen electrode depends on both the production of the corrosion scale and its peeling off. The oxygen generation on the alloy electrodes is also directly linked to the peeling off of the corrosion scale, resulting in the formation of corrosion powders in the electrolyte. For these Pb alloys, tin acts as an oxygen generation reducer and it may activate the production of the corrosion scale, which consists of PbO2 and PbSO4. Therefore, it seems that the increasing Sn content causes a decrease in the amount of the corrosion powder along with the growth of the corrosion scale. On the other hand, strontium has no influence on the corrosion resistance of the Pb–2mass% Sn–Sr alloy unless the Sr content is 0.46 mass% or more. The change in the crystal structure from a coarser columnar to a fine granular may account for the deterioration of the corrosion resistance at the Sr content of 0.46 mass% or more.
LiAl x Mn2−x O4 has been synthesized using various aluminum starting materials, such as Al(NO3)3, Al(OH)3, AlF3 and Al2O3 at 600–800°C for 20h in air or oxygen atmosphere. A melt-impregnation method was used to synthesize Al-doped spinel with good battery performance in this research. The Al-doped content and the intensity ratio of (311)/(400) peaks can be important parameters in synthesizing Al-doped spinel which satisfies the requirements of high discharge capacity and good cycleability at the same time. The decrease in Mn3+ ion by Al substitution induces a high average oxidation state of Mn ion in the LiAl x Mn2−x O4 material. The electrochemical behavior of all samples was studied in Li/LiPF6-EC/DMC (1:2 by volume)/LiAl x Mn2−x O4 cells. Especially, the initial and last discharge capacity of LiAl0.09Mn1.97O4 using LiOH, Mn3O4 and Al(OH)3 complex were 128.7 and 115.5mAh/g after 100 cycles. The Al substitution in LiMn2O4 was an excellent method of enhancing the cycleability of stoichiometric spinel during electrochemical cycling.
The increasing application of carbon paste electrode (CPE) in the fabrication of electrochemical sensors has motivated researchers to develop new electrode materials. In the present work, Fe3O4 nanoparticles supported on the multi-walled carbon nanotubes and polyacrylonitrile nanofibers (Fe3O4@MWCNTs@PANNFs) was synthesized via the bulk modification approach to detect imatinib (IMA), as an important anticancer drug. The modified CPE materials were characterized by FESEM, FT-IR, Raman spectroscopy, EDX analysis, XRD, CV, and EIS techniques. The electrocatalytic behavior of IMA at the surface of the modified CPE was studied using a differential pulse voltammetry method. Taking advantages of the electrocatalytic behavior of Fe3O4 nanoparticles and MWCNTs, as well as the large surface area of PANNFs, an applicable-modified CPE was introduced for electrochemical determination of IMA with high sensitivity. The anodic peak currents of IMA increased linearly within the concentration ranges of 0.0017–0.8500 μM, along with detection limits of 0.4 nM. In addition, the oxidation mechanism of IMA was proved by electrochemical simulation. Finally, the Fe3O4@MWCNTs@PANNFs/CPE was employed to the electrochemical determination of IMA in urine samples.
Despite many efforts devoted to explore novel electrode materials for lithium ion hybrid supercapacitors, the obtainable long-life cycling of existing anode materials are still inadequate for promising applications. This report demonstrates a new nanocomposite with TiNb2O7 network nanostructure in situ anchored onto the holey graphene, which is designed as anode material for lithium ion hybrid supercapacitors. Impressively, electrochemical analyses show that the good rate performance (capacity retention of 73.5% from 0.05 to 5 A g−1) and long cycle life up to 1000 cycles at 1 A g−1 (a capacity retention of 91.5%) are attained. Furthermore, the lithium ion hybrid supercapacitor device consisting of this nanocomposite and activated carbon exhibits excellent cycling stability (90.2% of initial capacity after 3000 cycles), high energy density of 86.3 W h kg−1 (at 237.7 W kg−1) and high power density of 3.88 kW kg−1 (at 28.7 W h kg−1). This study ascribes the unprecedented performance to the high conductive holey graphene with abundant mesopores, the uniformly distributed TiNb2O7 network nanostructure and the synergetic effect between them. Based on these findings, the presented nanocomposite has great potential in high performance lithium ion hybrid supercapacitors.
Two iron-based platinum group metal-free catalysts for the oxygen reduction reaction (ORR) were synthesized from novel and low cost organic precursors named niclosamide and ricobendazole. These catalysts have been characterized, incorporated in a gas diffusional electrode and tested in “clean” conditions as well as in operating microbial fuel cell (MFC) for 32 days. Both catalysts demonstrated unprecedented performance yielding a power density 25% higher than that of platinum (Pt) and roughly 100% higher than activated carbon (AC) used as a control. Durability tests were performed and showed that Pt-based cathodes lost their activity within the first week of operation, reaching the level of the supporting AC-based electrode. Fe–ricobendazole, however, demonstrated the highest performance during the long-term study with a power density of 195 ± 7 μW cm−2 (day 2) that slightly decreased to 186 ± 9 μW cm−2 at day 29. Fe–niclosamide also outperformed Pt and AC but the power density roughly decreased with 20% for the 32 days of the study. Accelerated poisoning test using S2− as pollutant showed high losses in activity for Pt. Fe–niclosamide suffered higher losses compared to Fe–ricobendazole. Importantly, Fe–ricobendazole represents a 55-fold cost reduction compared to platinum.
All-plastic dye-sensitized solar cells (DSSCs) using TiO2 paste (SP-210), indium tin oxide-coated polyethylene naphthalate (PEN/ITO) film and a Pt-coated PEN/ITO film counter electrode, were fabricated with 1.0wt% κ-carrageenan solid electrolyte containing the redox electrolytes ( I - / I 3 - ) solution. The cell performance of the all-plastic cell using 1.0wt% κ-carrageenan solid electrolyte was investigated in comparison with liquid type one, showing that the values of V oc (open circuit voltage) and ff (fill factor) were the same, but J sc (short circuit current) and η (conversion efficiency) were slightly larger for the liquid type electrolyte cell than the solid type one. A higher conversion efficiency was exhibited by UV-irradiation before heat treatment of the PEN/ITO/TiO2(SP-210) film than that after heat treatment. The effect of heat treatment conditions was investigated according to a modified hydrothermal treatment of the PEN/ITO/TiO2(SP-210) film, showing that the ff values become high (>0.7) by hydrothermal treatment. The electrochemical impedance spectroscopy (EIS) has shown the important comparison of each charge transport processes between the all-plastic and the conventional cells.
In typically developing children, researchers have found that anxiety disorders are associated with poorer intellectual abilities (Davis et al. Journal of Psychopathology and Behavioral Assessment 30:43–51, 2008). The aim of the current study was to examine the impact anxiety symptoms had on the developmental quotients of toddlers. A total of 170 toddlers ranging in age from 17 to 37 months were selected for inclusion in this study, all of whom were at risk for or had a developmental delay. Two factors indicative of behavioral symptoms of anxiety from the Baby and Infant Screen for Children with aUtIsm Traits-Part2 were utilized as the independent variables and the total developmental quotient from the Battelle Developmental Inventory, 2nd Edition was utilized for the dependent variable. Examination of results revealed that atypically developing toddlers with symptoms of anxiety had significantly lower developmental quotients when compared to toddlers without any anxiety symptoms. A discussion of the implications and limitations of this study are included.
This study emphasizes optimization of Fe2O3 and Fe3O4 nanowire conversion electrodes by directly-growing them on current collectors, preparing them as single crystals, and coating their surfaces with conductive carbon coatings. The systems with the least polarization during Li-ion cycling are then tested as electrodes for Na-ion chemistry. Precipitation of nanograined material during the first cycle reduces the polarization associated with Li insertion upon subsequent cycles. After the first cycle, delithiation primarily contributes to polarization associated with the conversion reaction with lithiation occurring close to the equilibrium potential. The initial reduction reaction does not proceed to completion for Na chemistries. Electron microscopy reveals significant Na insertion that occurs along with the formation of defect networks. However, the results indicate that an insufficient amount is present to form critical nuclei necessary to induce the conversion reaction.
The effect of morphine administration on immune parameters is well documented. However, there exists a limited knowledge of the effect of morphine's metabolites on immune status. The present study examines the immunomodulatory effects of the morphine metabolite, morphine-6β-glucuronide (M6G), in the rat and provides further evaluation of the antinociceptive effects of M6G. Animals were administered phosphate-buffered saline (PBS) or M6G in doses of 1.0, 3.16, or 10.0 mg/kg (subcutaneous (s.c.)) or 0.1, 0.316, or 1.0 μg (intracerebroventricular (i.c.v.)). Animals were tested for antinociception in the warm water tail-withdrawal procedure. In a separate set of animals, assessments of splenic natural killer cell activity, lymphocyte proliferative responses to mitogenic stimulation, and production of interferon-γ were made 1 h following the s.c. or i.c.v. administration of M6G. The results show that M6G induced potent antinociception that was evident for at least 120 min following administration. M6G also produced decreases in natural killer cell activity, lymphocyte proliferation, and interferon-γ production 1 h following both routes of administration. The difference in potency between immune alterations induced by subcutaneous vs. intracerebroventricular administration suggest central mediation of the immunomodulatory properties of M6G. Thus, M6G produces significant antinociception and immunomodulation in the rat. These findings demonstrate potent immunomodulatory properties of a metabolite of morphine, M6G.
In order to point out the effect of the support to the catalyst for oxygen reduction reaction nano-crystalline Nb-doped TiO2 was synthesized through a modified sol–gel route procedure. The specific surface area of the support, S BET, and pore size distribution, were calculated from the adsorption isotherms using the gravimetric McBain method. The support was characterized by X-ray diffraction (XRD) technique. The borohydride reduction method was used to prepare Nb–TiO2 supported Pt (20wt.%) catalyst. The synthesized catalyst was analyzed by TEM technique. Finally, the catalytic activity of this new catalyst for oxygen reduction reaction was investigated in acid solution, in the absence and the presence of methanol, and its activity was compared towards the results on C/Pt catalysts. Kinetic analysis reveals that the oxygen reduction reaction on Nb–TiO2/Pt catalyst follows four-electron process leading to water, as in the case of C/Pt electrode, but the Tafel plots normalized to the electrochemically active surface area show very remarkable enhancement in activity of Nb–TiO2/Pt expressed through the value of the current density at the constant potential. Moreover, Nb–TiO2/Pt catalyst exhibits higher methanol tolerance during the oxygen reduction reaction than the C/Pt catalyst. The enhancement in the activity of Nb–TiO2/Pt is consequence of both: the interactions of Pt nanoparticles with the support and the energy shift of the surface d-states with respect to the Fermi level what changes the surface reactivity.
KEYWORDS Personal Area Network, intra-body communication, analytical model, human body equivalent phantom, phase measurement
Li-ion batteries are prone to adverse physical and chemical mechanisms that can degrade their performance over time. For this reason, identifying each electrode's capacity and utilization window is important for the safe operation of the battery, unfortunately the standard capacity estimation method cannot provide this. In this work, we introduce electrode-specific State of Health (eSOH) related parameters, including individual electrode capacity and utilization window. We explore the identifiability of the parameters using terminal voltage alone and voltage plus cell expansion measurements. The analysis here is based on the constrained Cramer-Rao Bound (CRB) formulation, which provides the error bounds for the parameters. The model utilizes the voltage/expansion functions of lithium stoichiometry for the individual electrodes based on the underlying physics of phase transitions. It is shown that slope changes in voltage and expansion that correspond to phase transitions in the electrodes enhance the estimation. As a result, with the addition of the expansion, the parameters are estimable without the need to discharge the battery to a high Depth of Discharge ( > 70 % ), which rarely happens in automotive applications. This makes eSOH estimation feasible for a wider range of real-world driving scenarios.
For the purpose of biomonitoring, species that combine ecological and commercial importance may provide a link between ecological and human health risk. The common cuttlefish, Sepia officinalis, holds both characteristics in south-western Europe, albeit remaining unsurveyed in ecotoxicological studies. Cuttlefish collected from an impacted estuary in SW Portugal and a reference location off the coast were analysed for a battery of biomarker responses in the digestive gland and gills. The contrast to reference animals revealed that biomarker responses, especially those related to oxidative stress, were consistent with sediment contamination by PAHs, even in a situation that combines complex toxicant mixtures, moderate levels of contamination and high ecotoxicological diversity. However, environmental parameters related to the differences between shore and estuarine habitats should not be overruled. Also, digestive gland metallothionein retained significant specificity to metals even though previous studies in the area with clams and fish failed to trigger a conclusive response. The highest net differences in biomarker responses were detected in the gills, likely indicating higher sensitivity to environmental stressors. Still, the digestive gland responses were overall the most consistent with sediment contamination and effectively differentiated between estuarine industrial- and rural-impacted sites. The results indicate that S. officinalis may be a candidate to meet the European Union’s requirements for efficient biomonitoring programmes, with the additional importance of being cosmopolitan, abundant, commercially valuable and combining the molluscan biology that has been granting bivalves their high value for biomonitoring with foraging behaviour, thus better able to reflect anthropogenic stressors impacting a wider area than sedentary organisms. Nevertheless, further investigations in unpolluted sites are needed to better evaluate the background levels of biomarker responses in the species.
An on-chip fuel cell, of membraneless, air-breathing and monolithic design, was proven to operate on a different fuel (methanol, ethanol or 2-propanol) solution containing an acidic ion-conductor (sulfuric acid) or a neutral one (phosphate buffer).
A high-performance LiNi0.8Co0.2O2 cathode was successfully fabricated by a sol–gel coating of CeO2 to the surface of the LiNi0.8Co0.2O2 powder and subsequent heat treatment at 700°C for 5h. The surface-modified and pristine LiNi0.8Co0.2O2 powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), slow rate cyclic voltammogram (CV), and differential scanning calorimetry (DSC). Unlike pristine LiNi0.8Co0.2O2, the CeO2-coated LiNi0.8Co0.2O2 cathode exhibits no decrease in its original specific capacity of 182mAh/g (versus lithium metal) and excellent capacity retention (95% of its initial capacity) between 4.5 and 2.8V after 55 cycles. The results indicate that the surface treatment should be an effective way to improve the comprehensive properties of the cathode materials for lithium ion batteries.
The lithium–sulfur battery is promising as an alternative to conventional lithium-ion technology due to the high energy density of both sulfur and lithium metal electrodes. An extended lifetime has been demonstrated, but two notable challenges still exist to realize its full potential: to overcome the undesired high electrolyte/sulfur ratio required for the catholyte-type mechanism that governs most cell configurations, and to inhibit Li dendrite growth and its parasitic reaction with the electrolyte that results in cell degradation. Here, we demonstrate that by tuning the electrolyte structure, the challenges at both electrodes can be tackled simultaneously. Specifically, the sulfur speciation pathway transforms from a dissolution–precipitation route to a quasi-solid state conversion in the presence of a lowered solvent activity and an extended electrolyte network, curtailing the need for high electrolyte volumes. Ab initio calculations reveal the nature of the network structure. With such an optimized structure, the electrolyte allows dendrite-free Li plating and shows a 20-fold reduction in parasitic reactions with Li, which avoids electrolyte consumption and greatly extends the life time of a low electrolyte/sulfur (5 µl mg–1) sulfur cell.
SrHPO4 films were deposited on fluorine doped tin oxide coated glass (FTO) substrate by cathodic electrodeposition method for photoelectrocatalytic (PEC) oxidation of Rhodamine B (RhB). The as-prepared films were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy system (EDXS) and atomic force microscope (AFM). The effect of different parameters on the RhB electrochemical degradation, including supporting electrolyte type and concentration, current density, pH, and initial dye concentration, is studied. The most efficient conditions were found to be a current density of 10 mA cm−2, NaCl as a supporting electrolyte with a concentration of 0.1 M and a neutral medium which is favorable for HClO oxidizing species generation. Compared to photocatalysis and electrocatalysis, the photoanode displayed more superior photoelectrodegradation efficiency. Indeed, 94.5% removal of RhB (10 mg/L) in 12 min is obtained. This good efficiency is due to the synergetic effect induced by combining electrodegradation with UV-light energy. The reached electrocatalytic performance of SrHPO4 makes it a new promising photoanode for the treatment of wastewaters contaminated by organic pollutants.
A symmetric cell was adopted to analyze low temperature performance of Li-ion battery. Results showed that impedances of both Li-ion and symmetric cells are mainly composed of bulk resistance (R b), surface layer resistance (R sl) and charge-transfer resistance (R ct). Among these three components, the R ct is most significantly increased and becomes predominant as the temperature falls to below −10°C. Therefore, we may ascribe the poor low temperature performance of Li-ion battery to the substantially high R ct of the graphite and cathode. Comparing impedance spectra of the symmetric cells, we found that at −30°C the delithiated graphite and lithiated cathode, both of which correspond to a discharged state in a Li-ion battery, have a much higher R ct than when charged. This means that the Li-ion battery in the discharged state suffers a higher polarization. This result explains the phenomenon that at low temperatures, charging of a discharged Li-ion battery is more difficult than discharging of a charged battery.
Electrolyte imbalance is a major issue with Vanadium flow batteries (VFBs) as it has a significant impact on electrolyte utilization and cycle life over extended charge-discharge cycling. This work seeks to reduce capacity decay and prolong cycle life of VFBs by adopting a novel electrolyte-reflow method. Different current density and various start-up time of the method are investigated in the charge-discharge tests. The results show that the capacity decay rate is reduced markedly and the cycle life is prolonged substantially by this method. In addition, the coulomb efficiency, voltage efficiency and energy efficiency remain stable during the whole cycle life test, which indicates this method has little impact on the long lifetime performance of the VFBs. The method is low-cost, simple, effective, and can be applied in industrial VFB productions.
The effect of laser power on the Raman spectra of two carbon-coated nano-powders of LiCoPO4 and LiFePO4 olivine cathode materials were investigated. In the ambient atmosphere at a moderate laser power, the phenomenon of the removal of the carbon coating layer from both samples was detected. The olivine structure of LiCoPO4-C powder therefore remains unchanged during the prolonged exposure to a 4.3mW laser beam. The mild removal of the carbon layer makes it possible to analyze the details of the LiCoPO4 structure in air without interference from carbon. LiFePO4-C powder, together with carbon layer gasification, undergoes oxidative decomposition by the oxygen with the formation of Li3Fe2(PO4)3 and Fe2O3, even at a laser power of 1mW. Thus, care should be taken when measuring and interpreting the Raman spectra of this material both in air and in an inert atmosphere, as obvious decomposition of the LiFePO4 olivine structure takes place even at a moderate power of the excitation laser. A comparative study of the stability of these two carbon-coated nano powders under laser beam irradiation and heating was carried out with the use of TGA-mass spectrometry.