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The effect of alkali function group contained in electrode binder was investigated. Carboxy methyl cellulose (CMC) improved the initial irreversible capacity loss in graphite negative electrode. Lithium acetate also improved the initial cycle efficiency. On the other hand, ethyl cellulose (EC) and hydroxyl propyl methyl cellulose (HPMC), which do not have a carboxylic group, did not decrease the reductive electrolyte decomposition. After charge and discharge cycle, the surface film composition on the electrode with CMC was less than on the electrode without CMC. This suggests that a carboxylic group in the binder acted as a catalyst and promoted the solid electrolyte interphase (SEI) formation which prevents the excess electrolyte decomposition on the graphite electrode.
Salinity-gradient energy, also referred to as blue energy, is a largely untapped source of renewable energy. Coastal wastewater treatment plants discharge a continuous stream of low salinity effluent to the ocean and are thus attractive locations for recovery of blue energy. One method of tapping this gradient is a “mixing entropy battery” (MEB), a battery equipped with anionic and cationic electrodes that charges when flushed with freshwater and discharges when flushed with seawater. We constructed a plate-shape MEB, where the anionic electrode was Ag/AgCl, and the cationic electrode was Na4Mn9O18 (NMO). Over a single cycle with a single cell, the net energy recovery was 0.11 kW h per m3 of wastewater effluent. When twelve cells were connected in series, the net energy recovery (energy produced after subtracting energy invested) was 0.44 kW h per m3 of wastewater effluent. This is 68% of the theoretical recoverable energy of 0.65 kW h per m3 of wastewater effluent. We conclude that (1) wastewater effluent can be effectively used for charging of a MEB, (2) cells in series are needed to optimize net energy recovery efficiency, (3) there is a trade-off between net energy recovery efficiency and capital investment, (4) there is a trade-off between net energy recovery efficiency and power output, and (5) new electrode materials are needed to increase capacity, decrease cost, and to avoid release of Ag to seawater.
Based on Fourier’s law and the Seebeck effect, this paper presents a mathematical model of a Thermoelectric Generator (TEG) device using the exhaust gas of vehicles as heat source. The model simulates the impact of relevant factors, including vehicles exhaust mass flow rate, temperature and mass flow rate of different types of cooling fluid, convection heat transfer coefficient, height of PN couple, the ratio of external resistance to internal resistance of the circuit on the output power and efficiency. The results show that the output power and efficiency increase significantly by changing the convection heat transfer coefficient of the high-temperature-side than that of low-temperature-side. The results also show that with variation in the height of the PN couple, the output power occur a peak value, and the peak value decreases when decreasing the thermal conductivity of the PN couple, and increases when increasing the Seebeck coefficient and electric conductivity of the material. Meanwhile, a maximum output power and efficiency of a TEG appear when external resistance is greater than internal resistance. This is different from a common circuit, and with the increment of ZT, the maximum value moves toward the direction of an increasing ratio of external resistance to internal resistance. Finally, we propose a new idea to reform our experiment design to achieve better performance.
In this work, metallic copper serving as a high-performance cathode in lithium-ion based carbonate electrolyte has been demonstrated. Computational modelling and in-situ ultraviolet-visible spectra confirm that Cu cathode experiences a two-electrons redox reaction: Cu ↔ Cu2+ + 2e⁻ during charge/discharge process. By using one-dimensional (1D) nano-structure design and surface modification strategy, the Cu cathode delivers a reversible capacity of 635 mAh/gCu with a high output voltage of 3.61 V and affords a superior rate capability. With Li4Ti5O12 as anode, a Cu/Li4Ti5O12 full cell exhibits a discharge capacity of 601 mAh/gCu and an energy density of 1202 Wh/kgCu. The strategy of using metallic Cu as cathode in lithium-ion batteries is quite simple and broadly applicable, which may provide new opportunities for many other non-aqueous rechargeable batteries.
In order to further characterize reported deficits in affect perception in alcoholic Korsakoff patients, selected prosody subtests from the Tübingen Affect Battery were administered to seven Korsakoff patients and seven normal control participants. Results indicated that both linguistic and affective prosody discrimination were intact in Korsakoff patients. As well, affective prosody identification was unimpaired when the semantic content of the sentence was emotionally congruent with affective prosody. In contrast, affective prosody identification was significantly impaired when the semantic content was either neutral or incongruent with prosody. These results suggest that Korsakoff patients are impaired in interpreting the meaning of affective prosody in the absence of semantic cues as to the emotional content of sentences.
This paper has analyzed the case of Moushuni Island at Sundarban of 24 Parganas South of West Bengal, India. The proposition is to find out the possibility of grid-connectivity of Isolated Remote Island which is under rural electrification scheme by hybrid renewable energies under Jawaharlal Nehru National Solar Mission of India. In these rural electrification program, grid extension can be the best option if the grid is reliable, the rural community rather big and in proximity to the grid. In many circumstances, a strong case for mini-grids based on hybrid systems can be made. Scattered communities and isolated houses are well served by solar and small hydro (where available) or small wind energy systems. By feeding renewable electricity to the utility grid through the grid-connected hybrid renewable energy system, during time of peak demand, sufficient electrical loads can be shed to prevent turning on a coal or natural gas-fired plant and therefore save CO2 emissions and potentially energy import costs, replacing fossil fuels. The Social, Economic, and Environmental Benefits can be achieved through this proposition. Also, the Grid Interactive Operation of SPV System at Moushuni Island is tested. Malda district of West Bengal, India is a vision towards smart-grid city towards sustainable future, where rural consumers can upgrade their quality of life through solar energy resource.
Li0.5Ni0.25TiOPO4/C composite was synthesized by the co-precipitation method using polyethylene glycol as carbon source. X-ray diffraction study showed that the as-prepared material crystallizes in the monoclinic system (S.G. P21/c). This 3D structure exhibits an open framework favourable to intercalation reactions. The morphology and the microstructure characterisation was performed by scanning electron microscopy (SEM). Small particles (∼1μm) coated by carbon were observed. Raman study confirms the presence of carbon graphite in the Li0.5Ni0.25TiOPO4/C composite. Cyclic voltammetry (CV) and charge–discharge galvanostatic cycling were used to characterize its electrochemical properties. The Li0.5Ni0.25TiOPO4/C composite exhibits excellent electrochemical performances with good capacity retention for 50 cycles. Approximately 200mAh/g could be reached at C, C/2, C/5 and C/20 rates in the 0.5–3V potential range. These results clearly evidenced the positive effect of the carbon coating on the electrochemical properties of the studied phosphate.
Air stable copper phosphide of thicknesses (0.2, 0.4μm) was synthesized over copper plates (of 10mm diameter) by hybrid electrochemical deposition and low temperature solid-state reaction. Stoichiometric amount of red phosphorus (P) were sprayed over electrodeposited copper and followed by annealing at 250°C under inert gas atmosphere for different durations (5h, 7h and 12h). During this process, phosphorus particles diffuse by excavating into the copper deposits, producing holes, where the Cu3P crystallites nucleate and lead to conglomeration of several agglomerates and hence resulted in non-homogeneous morphology. A small extend of Cu3P oxidation occurs over the film's top surface. X-ray diffraction (XRD) patterns confirm that the layer to be pure Cu3P. Scanning electron microscopy (FEG-SEM) reveals a porous microstructure consisting of agglomerated particles with ∼10μm size. The as-prepared carbon-free Cu3P electrodes exhibited significantly improved capacity retention and rate capability characteristics over 40 cycles when electrochemically tested against lithium at constant 20μA/cm2 rendering it as possible negative electrode for high energy density lithium-ion battery (LiB) applications.
New surfaces were created by modifying gold electrode for electropolymerization of thiophene in aqueous media. The first step in modified electrode production was self assembled monolayer (SAM) coating. Thereby, surfaces with controllable chemical functionalities were obtained. The second step was gold nanoparticle (AuNP) deposition above this coating. Characterization of surfaces was made with electrochemical and spectroscopic methods. In this study, initially, the surface was insulated with inserting Au electrode into 11-mercaptoundecanoic acid (MUA) solution. Conductivity of surface was increased by gold nanoparticle deposition and gold nanoparticle pores were used as a platform for thiophene polymerization. Electropolymerization of thiophene in the aqueous media was achieved with the obtained modified electrode. At the end of study, voltammograms were taken in the 5mM Fe ( CN ) 6 4 - / 3 - redox probe containing 0.1M KCl and 0.1M HClO4 solutions. The characterization of modified surfaces was carried out by Scanning Electron Microscopy (SEM) and Attenuated Total Reflectance (ATR) methods.
The ability to optimize and tailor the properties of an electroceramic is one of the most challenging capabilities that an electroceramist must develop. Due to the fact that such a strong link exists between the microstructure of an electroceramic and its macroscopic electrical properties, significant efforts need to be made to control the factors and parameters that influence the characteristics of the microstructure. This chapter discusses the construction, utilization, and implementation of master sintering curves as specifically applied to electroceramics. The findings presented here demonstrate that a systematic approach to design, predict and control sintering of electroceramic systems is possible through the implementation of the master sintering curve.
We report on a novel differential electrochemical mass spectrometry (DEMS) set-up, which allows us the online detection of volatile products formed during potential induced decomposition of ionic liquids, and its application for elucidating the decomposition mechanism of the two ionic liquids (ILs) 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide ([BMP][TFSA]) and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ([EMIM][TFSA]) on polycrystalline Au electrodes. In the cathodic scan, the [BMP]+ cation decomposes at potentials more negative than −1.0V vs. Ag/AgCl by cleaving the butyl side chain, below −2.6V also ring opening takes place. For [EMIM][TFSA] reduction, we find a decomposition product which based on its mass is compatible with a stable imidazolium radical appearing at −2.3V, accompanied by its saturated derivative. In the anodic scan the [TFSA]− anion is decomposed first for both ILs, possible decomnposition products are discussed.
The time-independent and time-dependent mechanical behavior of electrochemically lithiated silicon was studied with nanoindentation. As indentation was performed with continuous stiffness measurements during loading and load-hold, new insight into the deformation behavior of lithiated silicon is furnished. Supporting other research, Young's modulus and the hardness of lithiated silicon are found to decline with increasing lithium content. However, the results of this study indicate that Young's modulus of the fully lithiated phase, at 41 GPa, is in fact somewhat larger than reported in some other studies. Nanoindentation creep experiments demonstrate that lithiated silicon creeps readily, with the observed viscoplastic flow governed by power law creep with large stress exponents (>20). Flow is thought to occur via local, shear-driven rearrangement at the scale of the Li15Si4 molecular unit volume. This research emphasizes the importance of incorporating viscoplasticity into lithiation/delithiation models. Additionally, more broadly, the work offers insight into nanoindentation creep methodology.
Soluble and insoluble inorganic additives have been applied to gel electrolytes in order to study possible enhancement of their characteristics and in this way extend the lifetime of lithium ion batteries. These additives consist of pure aluminum bromide (AlBr3) and/or fumed aluminum oxide (Al2O3) filler, pure and modified with H2SO4. These have been added to lithium perchlorate (LiClO4) dissolved in propylene carbonate (PC) giving, in result, electrolytes that can be soaked into PVdF/HFP-based membranes. According to theory, this certain type of additive should improve properties of the electrolyte. For comparison the addition of fillers with Lewis acid surface groups on the properties of gel electrolytes is shown. This article presents measurements of lithium transference numbers, stability of the passive layer between the metallic lithium and gel electrolyte, also spectroscopic measurements of the gel electrolytes have been performed.
Recent studies of lithium ion batteries focus on improving electrochemical performance of electrode materials and/or lowering cost. Doping of active materials with heteroatoms is one promising method. This paper reviews the effects of heteroatoms on anode materials such as carbon- and tin-based materials, and cathode materials such as LiCoO2, LiNiO2, LiMn2O4 and V2O5. There are favorable and unfavorable effects, which depend on the species and physicochemical states of heteroatoms and the parent electrode materials. In the application of lithium ion batteries advantageous factors should be exploited, unwelcome side effects should be avoided as far as possible. Considerable gains towards improved electrochemical performance of the electrode materials have been achieved. Nevertheless, there are still problems needing further investigation including theoretical aspects, which will in the meanwhile stimulate the investigation for better electrode materials.
Two-dimensional MoS2 is a promising candidate for high performance electrochemical capacitors. However, the understanding of different capacitive performances of MoS2 with different phases is still limited. Herein, the pseudocapacitive and electrical double layer characters in T and H phases of MoS2 monolayer are systematically studied, by using first-principles calculations and molecular dynamic simulations. The electronic levels referenced to the vacuum level are utilized to discuss the intrinsic pseudocapacitive characters. The large density of states of T-MoS2 located at 0.25V versus the standard hydrogen electrode indicates possible redox pseudocapacitance. Contrastively, the large band gap of H-MoS2 limits its pseudocapacitive behavior. Furthermore, the reaction with the Li atom is employed to shed more light on the possible redox behavior. The different shifts of Fermi levels in H and T phase confirm their different capacitive properties. Moreover, the electrical double layer capacitances character of MoS2 in aqueous solution is also investigated. The H-MoS2 exhibits similar double layer character with T-MoS2. The calculated double layer capacitances of MoS2 are comparable with graphene, and can reach 9.07μF/cm2 and 7.42μF/cm2 for anode and cathode, respectively. The combined calculations shed more light to explore other two-dimensional transition-metal dichalcogenides as supercapacitors electrode materials.
Herein, we report the synthesis of a novel imidazolium-based ionic salt, lithium (fluorosulfonyl) ((3-(1-methyl-1H-imidazol-3-ium-3-yl)propyl)sulfonyl) bis(fluorosulfonyl)imide (LiFSMIPFSI) as an electrolyte for the application in lithium-ion battery (LIB). The as-synthesized LiFSMIPFSI exhibited high purity and yield, which was characterized by various spectroscopic techniques. The LiFSMIPFSI electrolyte with a mixed solvent of ethylene carbonate (EC) and dimethyl sulfoxide (DMSO) (75:25 v/v) showed a wide electrochemical stability (ca. 4.5 V vs. Li/Li+) and high thermal stability (300 °C), good Li+ conductivity (ca. 8.02 mS/cm at 30 °C), and low intrinsic viscosity, which concurrently delivered a specific discharge capacity of ca. 125 mAhg−1 at 0.1 C with the full LIB configuration of LiFePO4/electrolytes/graphite. The performance of this LiFSMIPFSI electrolyte was enhanced further by the addition of conventional lithium bis(fluoro-sulfonyl)imide (LiFSI) and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) ionic salts (20% each) as additives with the specific discharge capacity of ca. 147 and 139 mAhg−1, respectively, at 0.1 C. This is mainly due to the additional enhancement of Li+ conductivity and its concentrations in the electrolytes induced by the additives. The LiFSMIPFSI electrolyte with LiFSI additive based LIB showed the highest cycling stability (capacity retention ca. 97%) among the electrolytes after 500 charge-discharge cycles. Thus, the present work contributes to the development of new ionic salts and its effects upon the addition of additives on LIB performance.
High performance composite of nanosized Li4Ti5O12 (LTO) and graphene nanosheets was fabricated using a novel atomic layer deposition (ALD) seeded process incorporated with hydrothermal lithiation for the first time. TiO2 nanoislands as seeds were anchored on graphene by ALD process, triggering the unique structure formation of subsequent LTO. The synergistic effects of nanosized LTO and graphene endow the composite with a short lithium ion diffusion path and efficiently conductive network for electron and ion transport, boosting the excellent reversible capacity, rate capability, and cyclic stability as anode materials for lithium ion capacitors (LICs). The reversible capacity of 120.8mAhg−1 at an extremely high current rate of 100C was achieved successfully, and the electrode can be charged/discharged to about 70% of the theoretical capacity of LTO in 25s. Meanwhile, the composite exhibited excellent cyclic stability of 90% capacity retention at 20C with nearly 100% Coulombic efficiency after 2500 cycles. The sintering treatment after hydrothermal reaction has significant effects on the crystallinity, defect density, microstructure and electrochemical property of the composite, which is also supported by theoretical calculations. The results provide a versatile roadmap for synthesis of high performance LTO based composite and new insights into LICs.
Tavorite-structured LiFePO4F is synthesized by solid-state reaction and characterized by Rietveld refined X-ray diffraction, scanning electron microscopy, BET surface area, IR and Raman spectroscopy techniques. The ionic conductivity (σ ionic) of LiFePO4F estimated using impedance analysis at 27°C and at 50°C are 0.6(±0.1)×10−7 and 5.4(±0.1)×10−7 Scm−1, respectively, with an energy of activation (E a)=0.75eV. Its electrochemical behavior were examined by galvanostatic charge–discharge cycling up to 100 cycles, cyclic voltammetry (CV) and electrochemical impedance spectroscopy using Li-metal as the counter and reference electrode, at 0.1C rate in the voltage range, 1.5–4V. LiFePO4F delivers an initial discharge capacity of 115(±3)mAhg−1 which increases to 119(±3)mAhg−1 at the 20th cycle. The capacity degrades slowly thereafter over 100 cycles, with a capacity loss of 19%. CV data show a clear indication of the Fe3+/2+ redox couple at 3.3–2.6V that involves a two-phase reaction. Electrochemical impedance spectra measured at various voltages at selected cycles were fitted to an equivalent circuit and the variation of impedance parameters interpreted.
Cadmium (Cd) is a heavy metal that can cause irreversible toxicity to animals, and is an environmental pollutant in farmlands. Spiders are considered to be an excellent model for investigating the impacts of heavy metals on the environment. To date, the changes at the molecular level in the cerebral ganglia of spiders are poorly understood. Cd exposure leads to strong damage in the nervous system, such as apoptosis and necrosis of nerve cells, therefore we conducted a transcriptomic analysis of Pardosa pseudoannulata cerebral ganglia under Cd stress to profile differential gene expression (DGE). We obtained a total of 123,328 assembled unigenes, and 1441 Cd stress-associated DEGs between the Cd-treated and control groups. Expression profile analysis demonstrated that many genes involved in calcium signaling, cGMP—PKG signaling, tyrosine metabolism, phototransduction–fly, melanogenesis and isoquinoline alkaloid biosynthesis were up-regulated under Cd stress, whereas oxidative phosphorylation-related, nervous disease-associated, non-alcoholic fatty liver disease-associated, and ribosomal-associated genes were down-regulated. Here, we provide a comprehensive set of DEGs influenced by Cd stress, and heavy metal stress, and provide new information for elucidating the neurotoxic mechanisms of Cd stress in spiders.
It is known that lead-cadmium alloys are very well hardened by a continuous precipitation and a discontinuous transformation, whereas lead-tin alloys present a discontinuous precipitation with a weak hardening effect. In these binary alloys, there is precipitation of either cadmium or tin. This study is focused on the type of precipitation, the nature and the morphology of the precipitated phases, and the intensity of hardening in ternary Pb-Cd-Sn alloys. The reequilibration of supersatured Pb-Cd-Sn alloys was studied by different experimental methods: hardness measurements, optical and electron microscopy, electron microprobe. Two structural states were considered: as-cast alloy, rehomogenised alloy. The alloys contain 1.5 wt% Cd and 0.25, 0.5 or 1.25wt% Sn. The explored temperatures were 20, 80 and 100 °C. The corresponding aging and overaging are similar to those of the Pb-Cd alloys. The presence of tin has a retarding effect on the structural hardening process.
One-dimensional (1D) vanadium pentoxide (V2O5) nanofibers (VNF) are synthesized by electrospinning vanadium sol–gel precursors containing vanadyl acetylacetonate and poly(vinylpyrrolidone) followed by sintering. Crystal structure, molecular structure and morphology of electrospun VNF are analyzed using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), selected area diffraction (SAED), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Single-phase electrospun VNF ∼300–800nm in diameter, 20–50μm long (aspect ratio>50) with porous interconnected fibrous morphology are revealed by FESEM and TEM analysis. Electrochemical properties of the sintered VNF, as a cathode in lithium-ion batteries, explored using cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) give rise to new understandings of the electrochemical processes occurring in these nanofibrous cathodes. Electrospun VNF exhibits initial discharge capacity ∼316mAhg−1 (∼2.2 Li per V2O5) in the voltage range of 1.75 and 4.0V vs. Li/Li+ at 0.1C rate. When cycled at a reduced voltage range of 2.0–4.0V vs. Li/Li+, less phase transitions occur, giving rise to the initial specific capacity of 308mAhg−1 and improved cyclic retention of 74% after 50 cycles.