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The electrochemical behavior of magnesium perchlorate in ionic liquids is characterized using Co3O4 as the working electrode and Mg foil as the anode material. The cations of the ionic liquids were 1,2-dimethyl-3-R-imidazolium with R =butyl (MMBI) or octyl (MMOI), and the anion was bis(trifluoromethanesulfonyl)imide (TFSI). The TFSI ionic liquids exhibited large electrochemical windows, with MMOITFSI possessing an electrochemical window of 5V. Ionic conductivity studies indicated a higher ionic conductivity of 3.67mS/cm for 1.0M Mg(ClO4)2 in MMBITFSI when compared to 2.16mS/cm for 1.0M Mg(ClO4)2. MMOITFSI was selected as the electrolyte for the electrochemical characterizations of Co3O4, due to its larger electrochemical window and its inability to intercalate, and therefore degrade, graphitic material added to the Co3O4 electrode. Electrochemical results indicated that the maximum attainable value for x in Mg x Co3O4 was 0.33, with an initial capacity of only 78mAh/g. X-ray diffraction studies of the Mg intercalated Co3O4 indicated a 20% expansion of the unit cell and a decrease in the symmetry of the metal oxide from cubic to orthorhombic symmetry. Charge/discharge experiments at a C/3 rate were performed vs. Mg metal. Results indicated that after 10 cycles, the capacity decreased linearly with cycling, most likely due to the inability to deintercalate the more strongly interacting Mg++.
Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4-based solution is used as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2, are used as the cathode. We show that a chemical conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This includes an operating voltage of 1.44 V, a capacity of 285 mAh g−1 (MnO2), and capacity retention of 92% over 5,000 cycles. The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-performance rechargeable aqueous batteries.
Cross-linked solid polymer electrolytes (cross-linked SPEs) composed of poly(ethylene glycol) dimethyl ethers (PEGDMEs) with various molecular weights and high molecular weight poly(ethylene oxide) (PEO), Acryl-HBP having various ethylene oxide (EO) units (3EO (n = 3), 4EO (n = 4), 6EO (n = 6), 11EO (n = 11)), and LiN(SO2CF3)2 salt were prepared by using radical initiator and electron beam (EB) irradiation. The effects of molecular weights of PEGDMEs and PEO, EO units in the Acryl-HBP, crosslinking methods, and EB irradiation intensity on the ionic conductivity and mechanical property for the cross-linked SPEs were investigated. Ionic conductivities of the cross-linked SPEs composed of Acryl-HBP having 4EO (n = 4) units and PEGDME with molecular weight of 500 were found to be 1.24 × 10−4 S/cm at 20 °C and 1.97 × 10−3 S/cm at 80 °C for benzoyl peroxide radical initiator and to be 2.44 × 10−4 S/cm at 20 °C and 3.22 × 10−3 S/cm at 80 °C for EB irradiation, respectively. Further addition of a copolymer (EO-AGE) of ethylene oxide with allyl glycidyl ether improved mechanical properties of the cross-linked SPE, and provided mechanical strength suitable for practical lithium battery application. The Li4Ti5O12/cross-linked SPE/LiFePO4–C cell was assembled by using the cross-linked SPE modified with EO-AGE, and the battery performance was evaluated. The battery showed reversible charge-discharge capacity of 42 mAh at 25 °C and C/10 rate.
Estuaries contain mosaic habitats which support fish across different life stages. Artificial reefs represent a form of habitat enhancement which can provide additional structure for fishes and improve fishing opportunities, but the role of artificial reefs within the broader estuarine seascape has not been extensively studied. We used a VEMCO Positioning System (VPS) to monitor the fine-scale movements of yellowfin bream (Acanthopagrus australis, referred to as Bream), an estuarine predator and important recreational species. Fish were implanted with acoustic tags with accelerometer sensors (to measure relative fish activity), and their movements monitored on an artificial reef and adjacent habitats. Elevated activity patterns during crepuscular periods indicated that foraging was likely occurring over a large seagrass bed adjacent to the artificial reef system. Alternatively, lower activity was observed when fish were on the artificial reef, which may reflect the role of this habitat as a refuge, or that alternative foraging strategies were being employed. All fish exhibited a high degree of fidelity to the artificial reef on which they were tagged, and there was minimal movement among other reef groups within the array. There was extensive overlap in space use contours for smaller fish on the seagrass edge, but no overlap for larger fish that also tended to forage further afield. These findings have implications for the way in which artificial reefs support fish production, especially the importance of connectivity with other key habitats within the estuarine seascape.
We simulate the electrochemical properties of Li-ion cells consisting of a blended cathode composed of LiMn2O4 and LiNi0.6Co0.2Mn0.2O2 and an artificial graphite anode using the Li-ion battery model available in COMSOL MULTIPHYSICS 4.4 along with a capacity fade model. The discharge profiles of the pure and blended cathodes at various current rates obtained through simulations and experimental results are well matched. By combining two capacity fade models available in literature, namely the solid electrolyte interphase (SEI) growth model and the Mn2+ dissolution model, the cycling performance of the pure LiMn2O4 cells at 25°C are successfully simulated and found to be in a good agreement with the experimental results. The blended cathode exhibits better capacity retention than the pure LiMn2O4 during cycling. We also observed that at high powers, the gravimetric energy density of the LiMn2O4 cathode exceeds that of the LiNi0.6Co0.2Mn0.2O2 cathode; the reverse effect is seen at low powers. Further, we were able to easily modulate the energy and power densities of the blended cathode system by changing the blend ratio in our simulation model.
The overvoltage that is produced in the cells under operation limits the capacity and power they can deliver. A detailed study about the mechanisms that contribute to that overvoltage—and thus to their lifetime—is required for optimizing the use of batteries as well as their manufacturing process. We investigate galvanostatic discharge at low and moderate rates in an LCO-NMC/graphite cell in order to quantify the ohmic voltage drop and activation and concentration polarizations. For doing so, we compare half-cells to full cell overvoltages. We find that the ohmic drop and concentration polarization dominate at high rates and low rates, respectively. Moreover, we track the evolution of concentration polarization with State-of-Charge (SoC) and we observe that there exists a relationship between diffusion and phase transformations. Specifically, we validate experimentally that initial stages of a phase formation are not dominated by diffusion. Phase transitions are commonly evaluated by incremental capacity analysis. However, we determine that it is more appropriate to obtain that information from the full cells by the overvoltage analysis. Furthermore, we suggest that the working SoC range can be optimized from the overvoltage analysis by avoiding the particular SoCs at which the most detrimental phase transitions take place.
The aims of this study were to investigate regional white matter microstructural differences between very preterm (VPT) (<30 weeks' gestational age and/or <1250 g) and full term (FT) (≥37 weeks' gestational age) infants at term corrected age with diffusion tensor imaging, and to explore perinatal predictors of diffusion measures, and the relationship between regional diffusion measures and neurodevelopmental outcomes at age 7 years in VPT children. Mean (MD) (p = .003), axial (AD) (p = .008), and radial diffusivity (RD) (p = .003) in total white matter were increased in VPT compared with FT infants, with similar fractional anisotropy (FA) in the two groups. There was little evidence that group-wise differences were specific to any of the 8 regions studied for each hemisphere. Perinatal white matter abnormality and intraventricular hemorrhage (grade III or IV) were associated with increased diffusivity in the white matter of VPT infants. Higher white matter diffusivity measures of the inferior occipital and cerebellar region at term-equivalent age were associated with increased risk of impairments in motor and executive function at 7 years in VPT children, but there was little evidence for associations with IQ or memory impairment. In conclusion, myelination is likely disrupted or delayed in VPT infants, especially those with perinatal brain abnormality (BA). Altered diffusivity at term-equivalent age helps explain impaired functioning at 7 years. This study defines the nature of microstructural alterations in VPT infant white matter, assists in understanding the associated risk factors, and is the first study to reveal an important link between inferior occipital and cerebellar white matter disorganization in infancy, and executive and motor functioning 7 years later.
Vanadium(V)-containing oxides show superior intercalation properties for alkaline ions, although the performance of the material strongly depends on its surface morphology. In this work, intercalation activity of LiV3O8, prepared by a conventional solid state synthesis, is demonstrated for the first time in non-aqueous Li,Na-ion hybrid batteries with Na as negative electrode, and different Na/Li ratios in the electrolyte. In the pure Na-ion cell, one Na per formula unit of LiV3O8 can be reversibly inserted at room temperature via a two-step process, while further intercalation leads to gradual amorphisation of the material, with a specific capacity of 190 mAhg−1 after 10 cycles in the potential window of 0.8–3.4 V. Hybrid Li,Na-ion batteries feature simultaneous intercalation of Li+ and Na+ cations into LiV3O8, resulting in the formation of a second phase. Depending on the electrolyte composition, this second phase bears structural similarities either to Li0.7Na0.7V3O8 in Na-rich electrolytes, or to Li4V3O8 in Li-rich electrolytes. The chemical diffusion coefficients of Na+ and Li+ in crystalline LiV3O8 are very close, hence explaining the co-intercalation of these cations. As DFT calculations show, once formed, the Li0.7Na0.7V3O8-type structure favors intercalation of Na+, whereas the LiV3O8-type prefers to accommodate Li+ cations.
A strategy has been developed to prepare conductive polymer-based nanocomposites as the electrode materials for supercapacitor with spent battery powder (SBP) as raw materials. Thus the waste resources from power could be sustainably recycled for new energy storage devices. The SBP containing manganese dioxide (MnO2) and graphite powder was obtained from the spent zinc-carbon battery, in which MnO2 was utilized for the oxidative polymerization of pyrrole. The binary graphite/polypyrrole (G/PPy) and ternary MnO2/graphite/polypyrrole (MnO2/G/PPy) nanocomposites were obtained under different reaction conditions, such as hydrochloric acid concentration, MnO2/pyrrole molar ratio, sodium p-toluene sulfonate (p-TSNa)/pyrrole molar ratio, and acid solution volume. The results showed that the electrochemical properties of the G/PPy nanocomposites were better than those of the MnO2/G/PPy. Under the optimized preparation condition (100mL of 1.5mol/L HCl with 0.03mol/L pyrrole, and MnO2/pyrrole/p-TSNa molar ratio of 1:1:1), the G/PPy nanocomposite possessed a relatively high Coulombic efficiency, a high electrical conductivity of 20.0S/cm, and the highest specific capacitance of 212.4F/g at 1mV/s scan rate tested by CV, as well as a retention of 89.5% of its original capacitance after 1000 cycles.
Virtual reality (VR) has made it possible for users to access novel digital experiences. An interesting question that arises in the context of VR is whether it appears or feels different to users when different virtual environments are used. This study investigates the effect of VR head-mounted display (HMD) and desktop computer-facilitated VR on users’ sense of presence (spatial presence and immersion) and task-oriented self-efficacy when exposed to an earthquake education VR system. A quasi-experiment design was used with a sample of 96 university students. The results revealed that the VR system had positive impacts on the users’ earthquake preparedness self-efficacy. Although the experiment group (n = 39) had repeated experiences, as they first used desktop VR followed by VR HMD for the same content, users indicated a higher sense of spatial presence and immersion while using VR HMD than when using desktop VR. In addition, a VR HMD single-group pre- and posttest experimental design was performed with 20 participants, and the differences between the pretest and posttest measurements of earthquake preparedness and self-efficacy were determined to be significant. The qualitative results reveal that the visual stimulus and motion are relevant in composing the VR experience.
An in situ electrochemical atomic force microscopy (AFM) observation of a composite graphite electrode surface was performed in 1moldm−3 LiClO4 dissolved in a mixture of ethylene carbonate (EC)+diethyl carbonate (DEC), and propylene carbonate (PC) to show the applicability of scanning probe microscopy (SPM) to studies using composite graphite electrodes. In EC+DEC, three kinds of morphological changes (curling, swelling, and exfoliation) in the vicinity of the particle edges were observed in the potential range of 0.8–1.4V versus Li+/Li. These morphological changes were caused by the intercalation of solvated lithium ions and their subsequent decomposition between graphene layers. On the other hand, vigorous exfoliation and rupturing of graphene layers of the graphite particles were observed at 0.9V in PC. In addition, deterioration by the formation of holes in the composite graphite electrode was observed in PC, which is attributable to gas evolution upon decomposition of PC molecules.
We used a battery of genes encoding transcription factors (Pax6, Islet1, Nkx2.1, Lhx6, Lhx5, Lhx9, FoxP2) and neuropeptides to study the extended amygdala in developing zebra finches. We identified different components of the central extended amygdala comparable to those found in mice and chickens, including the intercalated amygdalar cells, the central amygdala, and the lateral bed nucleus of the stria terminalis. Many cells likely originate in the dorsal striatal domain, ventral striatal domain, or the pallidal domain, as is the case in mice and chickens. Moreover, a cell subpopulation of the central extended amygdala appears to originate in the prethalamic eminence. As a general principle, these different cells with specific genetic profiles and embryonic origin form separate or partially intermingled cell corridors along the extended amygdala, which may be involved in different functional pathways. In addition, we identified the medial amygdala of the zebra finch. Like in the chickens and mice, it is located in the subpallium and is rich in cells of pallido-preoptic origin, containing minor subpopulations of immigrant cells from the ventral pallium, alar hypothalamus and prethalamic eminence. We also proposed that the medial bed nucleus of the stria terminalis is composed of several parallel cell corridors with different genetic profile and embryonic origin: preoptic, pallidal, hypothalamic, and prethalamic. Several of these cell corridors with distinct origin express FoxP2, a transcription factor implicated in synaptic plasticity. Our results pave the way for studies using zebra finches to understand the neural basis of social behavior, in which the extended amygdala is involved.
Lithium-rich layered cathode Li1.2Mn0.54Ni0.13Co0.13O2 is synthesized by a co-precipitation method followed by high-temperature treatment and surface coated with different amount of amorphous FePO4. The microstructure and electrochemical performance of the as-prepared cathode materials are investigated systematically. It is demonstrated that the Li1.2Mn0.54Ni0.13Co0.13O2 particles are uniformly coated with amorphous FePO4. With proper amount of amorphous FePO4 coating layer, significant improvements in discharge capacity, initial Coulombic efficiency, rate capability, cycle performance, and thermal stability are achieved at room temperature. Specifically, the 3 wt.% FePO4-coated cathode exhibits the highest discharge specific capacities (271.7 mAh g−1 at C/20), improved initial Coulombic efficiency (85.1%), and best cyclability (discharge capacity of 202.6 mAh g−1 at C/2 after 100 cycles), while the 1 wt.% FePO4-coated cathode displays the best rate capability (194.3 mAh g−1 at 1 C rate and 167.9 mAh g−1 at 2 C rate). The charge–discharge curves and electrochemical impedance spectra reveal that the improved electrochemical performances are due to the suppression of both the oxygen vacancy elimination at the end of the first charge and side reactions of the cathode with the electrolyte, as well as the decrease in charge transfer polarization by the FePO4 coating layer.
The utilization of the stream of waste secondary nickel-metal hydride (Ni-MH) and lithium-ion (Li-ion) cells, representing annually about 33% of all consumer batteries and accumulators placed on the Polish market, will soon become a big challenge for both legislators and plants dealing with the recycling of this type of hazardous waste. It is due to the fact that no company in Poland operating on the market has a complete technology for the processing of a full stream of waste chemical energy sources produced in this country. Until now, the most commonly used techniques of processing this type of waste were pyrometallurgical process. In this paper, the quantitative and qualitative characteristics of the stream of waste batteries and accumulators collected at separate collection points are presented. The results of metal recovery: caesium, lanthanum, cobalt, iron, manganese, nickel and zinc from the stream of waste Ni-MH cells, type R6 (AA), using hydrometallurgical methods are also offered. The paper demonstrates that one-stage leaching at an initial temperature of 25.0 °C, with 3 M H2SO4 and at the solid to liquid ratio of s/l = 1/10, within 75 min, at a mixing speed of 500 rpm and in a strongly acidic environment should be adopted as optimal parameters for acid leaching of the paramagnetic fraction created after mechanical machining of Ni-MH battery, for which the leaching rates of individual metals were as follows: Ce - 97.7%, La - 88.7%, Co - 79.4%, Fe - 68.5%, Mn - 91.9%, Ni - 66.2% and Zn - 100%.
Surface structure and electrochemical behavior of surface-fluorinated petroleum coke samples (original petroleum coke and those heat-treated at 1860, 2300 and 2800°C, abbreviated to original PC, PC1860, PC2300 and PC2800, respectively) have been investigated. Surface fluorination of petroleum cokes by elemental fluorine reduced surface oxygen. Surface areas of fluorinated petroleum cokes were nearly the same as those of non-fluorinated ones or only slightly increased by fluorination except original PC fluorinated at 300°C. Total meso-pore volumes of fluorinated samples showed the same trend. The charge capacity of non-fluorinated petroleum coke was increased by heat-treatment at 2300 and 2800°C. However, the first coulombic efficiency was the highest, 90–89% in PC1860, decreasing to 72–70 and 65–64% for PC2300 and PC2800, respectively. It is noted that first coulombic efficiencies were increased by 12–18% for PC2300 and PC2800 fluorinated at 300°C.
Publisher Summary This chapter focuses at what ‘correct’ exposure means and what one should aim for using different films. It discusses equipment for measuring and setting exposure, their different modes of use, and how to avoid mistakes with problem subjects. Films or digital image chips need to receive just the right amount of light to record an image. If insufficient light reaches them they record nothing, or a dark, partial picture. Similarly, too much exposure results in a bleached, washed-out image or just a white blank. “Giving the right exposure” means capturing the correct amount of image light (photons). In practice it is much more than this. Exposure can be used to give emphasis, by deliberately over- or under-exposing parts of the scene such as backgrounds to draw the eye towards the main subject or particular areas and therefore affect composition. Exposure control is also the key to getting fine tonal qualities in the final pictures, whether prints or slides.
We propose a new direct methanol fuel cell with a zigzag-folded membrane electrode assembly. This fuel cell is formed by a membrane, which is made up of anode and cathode electrodes on a zigzag-folded sheet, separated by insulation film and current collectors. Individual anodes, cathodes and membranes form a unit cell, which is connected to the adjacent unit cell. The fuel cell can achieve high output voltage through easy in-series connection. Since it is not necessary to connect electrodes, as in the manner of conventional bipolar plates, there is no increase in fabrication cost and no degradation in reliability. The fuel feeds for the anode and cathode are achieved through methanol and air feeds on each electrode, which do not require electricity to run a pump or blower. The experimental cells were formed with an active area of 16cm×2cm on membrane-folded cells. Filter papers with slits were inserted between anodes to improve their methanol supply. A power density of 3mWcm−2 was obtained at a methanol concentration of 2M at ambient temperature. The cell power was affected by the slit area on cathode.
Ultra-stable anode materials for lithium-ion batteries are increasing in demand as highly sustainable energy storage system with excellent charge transport becomes unprecedentedly important. Here, a novel Li-ion full cell, utilizing BNb3O9 hollowed-out nanobelts as the typical intercalation anode and commercial LiFePO4 as the cathode in organic electrolyte, is reported. Moreover, the hollowed-out framework of BNb3O9 nanobelts, prepared by an adjustable-voltage electrospinning method, exhibits prominent cyclic stability (116.1 mAh g−1 at 700 mA g−1 (12C) over 1000 cycles) and outstanding rate capability (126.8 mAh g−1 at 900 mA g−1) in half cell. The key finding is that the formation mechanism of BNb3O9 hollowed-out nanobelts can be thoroughly discussed by scanning electron microscope. The contribution of the external pseudocapacitance largely affects the rate capability, which is determined via kinetic analysis. Furthermore, the lithium storage mechanism and structural evolution of BNb3O9 are investigated through in-situ X-ray diffraction. Such preeminent electrochemical performance and distinctive morphology endow BNb3O9 hollowed-out nanobelts with potentials as anode materials for lithium-ion batteries.