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The electrochemical reaction mechanism of the Sn–(CaSiO3)0.4 composite electrode with Li was investigated by electrochemical tests and a variety of spectroscopic techniques. The electrochemical behavior of this material showed a highly reversible reaction with Li after the first discharge with a specific capacity of 530mAhg−1 at C/10 rate. Some essential steps of the mechanism have been inferred from 119Sn Mössbauer spectroscopy and the electrochemical potential curve. The composite material contains three tin based phases with different tin oxidation numbers: an amorphous SnII phase which is reduced into Sn0 as the first step of the discharge, CaSnIVSiO5 and β-Sn which are progressively transformed into lithium–tin alloys during the discharge. A Mössbauer spectrum recorded at the end of the discharge reveals the formation of Li7Sn2. The de-alloying reaction of Li7Sn2 leads to the formation of β-Sn at the end of the charge. X-ray absorption and 119Sn Mössbauer spectroscopy revealed furthermore that the electrochemical reaction between Li and the Sn–(CaSiO3)0.4 composite is accompanied by an electron transfer between Li and Sn.
Publisher Summary This chapter discusses different types of lead-acid secondary batteries, such as stationary type or standby power batteries, traction power type, automotive batteries, and electric vehicle batteries. The choice of a standby system lies between batteries, usually lead-acid or nickel-cadmium, and generators, or a combination of the two. Large battery installations which are called upon only occasionally to supply power, usually in emergency or auxiliary power supply circumstances, are referred to as stationary or standby batteries. For many applications, the battery's ability to provide the power required instantly makes it more suitable. Partially recombining sealed lead-acid batteries are used in either cyclic or float service in a wide range of applications. The batteries feature lead-calcium alloy grids for achieving long and reliable service and also a suspended electrolyte system. These batteries are available in capacities between 5 and 50 A h.
This work focuses on fabrication routes and performance evaluation of thin form-factors, reserve cells, as a powering alternative for expendable and/or remotely operated systems. The catalytic decomposition of sodium hypochlorite solutions is revisited herein with two cost-effective anodes: zinc and aluminum. Aluminum, even though the most expensive of the utilized anodes, constituted cells with double the energy content (up to 55Whkg−1) than those fabricated with zinc. Even though the hypochlorite concentration in the solution limits the cells’ operational life, attractive performances (1.0V with a current of 10mA) for the manufactured cells are obtained. It is shown that micro fabrication processes, allowing for close electrodes interspacing, provided high faradic and columbic efficiencies of up to 70 and 100%, respectively. Obtained specific energies (50–120Whkg−1) are in the same order of magnitude than batteries currently used for powering deployable systems. Experimental results show that a simple model that linearly relates over potentials and the electrical load, adequately describe all the cell designs. A mathematical model based on a kinetic–mechanistic scheme that relates the current output as a function of time agrees fairly well with results obtained activating cells with various concentrations of NaOCl solutions.
Publisher Summary This chapter provides an insight into general principles associated with the transportation of hazardous substances. Transportation of a chemical between the supplier and/or agent and the user may introduce special risks in addition to those which can arise from the inherent chemical and physical properties. Comprehensive labeling and identification procedures and information supply aim to avoid any confusion over the nature of the chemical and recommended handling, storage, and emergency procedures. However, different parties have to oversee, and take responsibility for, the chemical at different stages during its movement between sites, for example loading/storage, transport by various methods, storage in transit, and unloading. Moreover, third parties can be prone to injury, and property or the environment can be subjected to damage if loss of containment occurs.
In this study, ZnO nanorod arrays have been evaluated for the negative electrodes of lithium-ion batteries. The ZnO nanorod arrays with dandelion-like morphology were directly grown on copper substrates by a hydrothermal synthesis process at 80°C. X-ray diffraction, scanning electron microscopy, galvanostatic discharge–charge, and cyclic voltammetry were employed to characterize the structure and electrochemical property of the arrays. The array electrodes showed a stable capacity over 310mAhg−1 after 40 cycles, and good capacity retention as the anodes of lithium-ion batteries. It was believed that the unique dandelion-like binary-structure played an important role in the electrochemical performance of the array electrodes. The present finding opens the possibility to fabricate micro/nanometer hierarchical ZnO films that might be applied in lithium-ion batteries.
In this study, Li3V2(PO4)3/carbon samples were synthesized by two different synthesis routes. Their influence on chemical and electrochemical performances of Li3V2(PO4)3/carbon as cathode materials for lithium-ion batteries was investigated. The structure and morphology of Li3V2(PO4)3/carbon were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM) measurements. TEM revealed that the Li3V2(PO4)3 grains synthesized through the sol–gel route had a depressed grain size. Electrochemical behaviors were characterized by galvanostatic charge/discharge, cyclic voltammetry and AC impedance measurements. Li3V2(PO4)3/carbon with smaller grain size showed better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of the Li3V2(PO4)3/carbon were attributed to the depressed grain size and enhanced electrical contacts produced via the sol–gel route. AC impedance measurements also showed that the sol–gel route significantly decreased the charge-transfer resistance and shortened the migration distance of lithium ion.
The important energy requirements for the desalination process impose especially in autonomous and decentralized plants supplied by Renewable Energy Sources (RES). In this paper, five alternative energy generation topologies of Reverse Osmosis desalination process are evaluated. The proposed topologies assessed in terms of economic, environmental, technological and societal indices are compared using multi-criteria analysis, namely the Analytic Hierarchy Process (AHP) and the Preference Ranking Organization Method for Enrichment of Evaluations (PROMETHEE). Ranking of topologies resulted in the selection of direct connection and hybrid configuration as optimum solutions. In case economic priorities prevail diesel generation should also be considered.
The influence of cycling rate and temperature on the performance of lithium sulfur batteries is systematically studied by evaluating data of hundred identical cells. Differences in the discharge and charge capacities and the voltage profiles during the first and subsequent cycles are evaluated quantitatively in detail. Special attention is paid to the parasitic shuttle effect and its magnitude as function of C-rate and temperature. Mathematical models by Kumaresan et al. and Mikhaylik et al. are used to discuss the correlation between discharge/charge capacities, cycling efficiency and cycling rate at different temperatures. Mathematical error analysis further provides information on typical deviations between identical samples that can be expected when characterizing Li/S cells. This error can become significant especially when reaching higher cycle numbers. When changing the cycling parameters we find that the different regions of the voltage profile are affected differently. Therefore, we conducted first galvanostatic intermittent titration technique (GITT) measurements on the Li/S cell system to study the kinetics during cell cycling and evaluated the relaxation behavior between the different states of discharge/charge and OCV conditions. Significant differences in relaxation kinetics are found for the lower and higher plateaus of the discharge- and charge voltage profiles.
The high-temperature charge acceptance of Ni-MH batteries has been improved through the addition of calcium fluoride to the pasted nickel hydroxide electrode made using spherical Co(OH)2-coated nickel hydroxide powder. The charge acceptance of the Ni-MH battery at 60°C is over 95% at 1C charge/discharge rates. The charge acceptance at 60°C remains at over 90% through 10 cycles. The use of Co(OH)2-coated Ni(OH)2 plus a CaF2 addition to the positive electrode also significantly improved the high-temperature stability in terms of reduced gas evolution.
We recently developed a telemetry system for recording neural activity in the brains of unrestrained pigs. To test the fidelity of waveform reproduction, we compared local field potentials in the temporal hippocampus of six pigs by simultaneous recording with a cable system. We analyzed differences between the telemetry and cabled data filtered through a low-cut filter at 1, 4, or 30Hz. Analysis of 10,000 data recorded while pigs were lying down showed a higher correlation with low-cut filtering at 4 or 30Hz than at 1Hz. Over 97% of differences in amplitude between the telemetry and cable data lay within the 95% confidence interval. Measurements were reproducible. A box plot of the differences clearly showed increased data symmetry and reduced skewness by low-cut filtering at 4 or 30Hz. Almost the same results were obtained in two animals during feeding. Thus, the local field potentials in the temporal hippocampus were telemetered with almost the same accuracy as by cable measurement during both resting and feeding. However, artifacts in the first 100ms (low-cut filtering at 1 or 4Hz) or 5ms (30Hz) of measurements had to be removed for analysis.
Vanadium flow battery is emerging as one of the most promising candidates for large scale energy storage application. The major restriction on the route to commercialization is the high cost of the system. One of the effective ways to lower the cost of a vanadium flow battery system is improving the power density by reducing the battery polarization, which can be realized by controlling the electrode compression ratio reasonably. An overall polarization model, in consideration of the ohmic loss, activation loss and mass transport loss, was proposed for the first time. Then, the polarization model was coupled with a previously developed three-dimensional model to obtain a mechanistic understanding of the relationship between the electrode compression ratio and battery polarization. By combining numerical simulation with experiments, the effect of the compression ratio on the polarization and subsequently the battery performance was explored systemically and deeply, and the performance superiority of the battery assembly with the obtained optimal compression ratio was verified by experiments.
Spherical Li[Ni1/3Co1/3Mn1/3]O2 powders were synthesized from LiOH·H2O and coprecipitated spherical metal hydroxide, (Ni1/3Mn1/3Co1/3)(OH)2 and coated with Al(OH)3. The Al(OH)3-coated Li[Ni1/3Co1/3Mn1/3]O2 showed a capacity retention of 80% at 320mAg−1 (2C-rate) based on 20mAg−1 (0.1C-rate), while the pristine Li[Ni1/3Co1/3Mn1/3]O2 delivered only 45% at the same current density. Also, unlike pristine Li[Ni1/3Co1/3Mn1/3]O2, the Al(OH)3-coated Li[Ni1/3Co1/3Mn1/3]O2 cathode exhibits excellent rate capability and good thermal stability.
Hierarchical β-Ni(OH)2 hollow microspheres with partial open gaps have successfully been prepared via a facile hydrothermal process with the assistance of l-lysine. The as-prepared products have been characterized by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption/desorption, respectively. The results reveal that the sample consists of a large scale of porous microspheres which is composed of nanosheets. A possible growth mechanism is proposed including the initial formation of hierarchical hollow microspheres aggregated from nuclei and the subsequent site-specific oriented growth of nanosheets by self-assembly along a preferred growth direction of [101] at the growth state. It is found that l-lysine used as a crystal growth modifier plays a key role in the formation of this hierarchical structure. This special structure is also responsible for the obvious enhancement of electrochemical properties, which exhibits a high specific capacitance of 1398.5Fg−1 at a current density of 5mAcm−2 and excellent cycling stability. This hollow microspheres display great potential as electrode materials for electrochemical capacitors.
Homogeneous and transparent film-shaped spinel Li4Ti5O12 electrodes on gold coated quartz were synthesized by sol–gel and a dipping procedure after thermal treatments at 700°C. The influence of the lithium precursor content on the phase composition, structure and electrochemical behavior of this material was studied. Spectral ellipsometry measurements and SEM-EDX analysis indicate an average thickness between 385 and 560nm. Rutile TiO2 is detected using grazing incidence X-ray analysis and Micro-Raman in compositions with a lower content of lithium. Good galvanostatic cycling and very flat discharge–charge profiles confirm the high purity of Li4Ti5O12 electrodes obtained with the higher lithium content composition.
Yolk@shell nanocomposites with delicate composition and tailored structure usually exhibit great potential in various areas. In the present study, the synthesis of yolk@shell Fe3O4@MnO2 microspheres was reported using core@shell Fe3O4@polydopamine (Fe3O4@PDA) as starting materials. This novel approach is based on the reductive property of the PDA derived carbon shell. The new shell of MnO2 was synthesized by reaction of PDA derived carbon and KMnO4. The Fe3O4@MnO2 yolk@shell microsphere was successfully used as electrode material for supercapacitor and delivers a high specific capacitance of 715 F/g at 1 A/g with a good rate capability (450 F/g at 10 A/g). Furthermore, the Fe3O4@MnO2 yolk@shell microsphere was also used as the positive electrode for asymmetric supercapacitors (ASC), wherein N doped carbon from PDA was applied as negative electrode. As a result, the energy density of the constructed ASC device was up to 31.3 Wh/kg at a power density of 750 W/kg. Meanwhile, the Fe3O4@MnO2//N-pC (PDA derived N-doped porous carbon) device offers an excellent cycling stability (94.7% of capacitance retention after 5000 cycles). Such distinguish capacitive performance is undoubtedly related to the electrochemical actuation of the yolk@shell microsphere structure and their structural integrity, where the void between the shell and yolk may relieve the volume change of the electrode. Considering the efficiency and simplicity of the synthetic procedure, it is expected that the present method might be suitable for preparation of yolk@shell composite with other components and structures, offering potential in various applications.
LiCoO2 thin films with nanosize particles were synthesized on Au substrates by nanosheet restacking method and subsequent hydrothermal reaction which needs less cost than the vacuum deposition methods. The grain size of LiCoO2 films estimated by XRD reflection was about 15nm that was independent of the thickness of precursor cobalt hydroxide film. Comparing the rate performance of the thin films with various thickness, the optimum performance was obtained by the thin film with 5min deposition time: 62% of the capacity was held at 400 C-rate compared with that at 20 C-rate. The results of AC-impedance analysis of electrode reaction indicate that the high rate capability of the LiCoO2 film is obtained by the small grain size and large surface area of LiCoO2 thin film with nano size particles.
Electrochemical capacitors, also known as supercapacitors, are becoming increasingly important components in energy storage, although their widespread use has not been attained due to a high cost/performance ratio. Fundamental research is contributing to lowered costs through the engineering of new materials. Currently the most viable materials used in electrochemical capacitors are biomass-derived and polymer-derived activated carbons, although other carbon materials are useful research tools. Metal oxides could result in a step change for electrochemical capacitor technology and is an exciting area of research. The selection of an appropriate electrolyte and electrode structure is fundamental in determining device performance. Although there are still many uncertainties in understanding the underlying mechanisms involved in electrochemical capacitors, genuine progress continues to be made. It is argued that a large, collaborative international research programme is necessary to fully develop the potential of electrochemical capacitors.
The purpose of this study consists of analyzing the existing correlations between the simple reaction time (measures the speed of the nervous influx), the discrimination reaction time (measures the speed of the nervous influx combined with the identification time), the decision time (the necessary time needed for the mental operation of identification), vigilance and the sports performance of elite Romanian junior tennis players. The TR and VIGILANCE tests, included into the PSISELTEVA battery, developed by RQ Plus, evaluates the simple reaction time, the discrimination reaction time and vigilance. The subjects who took part in this study are 12 elite junior tennis players. Using the Spearman correlation there have been important relations highlighted between the decision time, vigilance and the sports performance, expressed through the ranking position (the official ranking system).
Battery state-of-charge (SoC) and state-of-power capability (SoP) are two of the most significant decision factors for energy management system in electrified vehicles. This paper tries to make two contributions to the existing literature. (1) Based on the adaptive extended Kalman filter algorithm, a data-driven joint estimator for battery SoC and SoP against varying degradations has been developed. (2) To achieve accurate estimations of SoC and SoP in the whole calendar-life of battery, the need for model parameter updates with lowest computation burden has been discussed and studied. The robustness of the joint estimator against dynamic loading profiles and varying health conditions is evaluated. We subsequently used data from cells that have different aging levels to assess the robustness of the SoC and SoP estimation algorithm. The results show that battery SoP has close relationship with its aging levels. And the prediction precision would be significantly improved if recalibrating the parameter of battery capacity and resistance timely. What's more, the method reaches accuracies for new and aged battery cells in electrified vehicle applications of better than 97.5%.
Aqueous rechargeable batteries (ARBs) based on migration of two types of shuttle ions not only enrich the battery families but also make it more available for ARBs with operation potential higher than 1.2V. In this paper, we report on electrochemical properties of ARBs in configuration of NaTi2(PO4)3/C||LiMn2O4, i.e. NTP/C||LMO. NTP/C was prepared through a simple and scalable co-precipitation post annealing treatment method and featured with hierarchical structure, high specific surface area, and abundant mesopores. The electrochemical properties of individual anode and cathode were examined in 1molL−1 Li2SO4, 1molL−1 Na2SO4, and 0.5molL−1 Li2SO4/0.5molL−1 Na2SO4 mixed electrolyte, respectively. It is found that NTP/C exhibits superior operation in 1molL−1 Na2SO4 and inferior operation in 1molL−1 Li2SO4 while the situation is contrary for LMO. However, NTP/C||LMO full cells with Li+/Na+-mixed electrolyte exhibit enhanced electrochemical performance, presenting an anode-dependant electrochemical behavior. When operating at 1C, NTP/C||LMO with Li+/Na+-mixed electrolyte can deliver a discharge specific capacity (C dis) of 104.6mAhg−1 based on the weight of NTP/C, and a specific energy (E cell) of 59.5Whkg−1 with corresponding specific power of 76.8Wkg−1 based on the total weight of active electrode materials. After 220 cycles at 1C, the C dis and E cell remain 75.7mAhg−1 and 43.0Whkg−1, respectively.
In this paper, an innovative approach is presented to optimize the flow rate of a 6-kW vanadium redox flow battery with realistic stack dimensions. Efficiency is derived using a multi-physics battery model and a newly proposed instantaneous efficiency determination technique. An optimization algorithm is applied to identify optimal flow rates for operation points defined by state-of-charge (SoC) and current. The proposed method is evaluated against the conventional approach of applying Faraday's first law of electrolysis, scaled to the so-called flow factor. To make a fair comparison, the flow factor is also optimized by simulating cycles with different charging/discharging currents. It is shown through the obtained results that the efficiency is increased by up to 1.2% points; in addition, discharge capacity is also increased by up to 1.0 kWh or 5.4%. Detailed loss analysis is carried out for the cycles with maximum and minimum charging/discharging currents. It is shown that the proposed method minimizes the sum of losses caused by concentration over-potential, pumping and diffusion. Furthermore, for the deployed Nafion 115 membrane, it is observed that diffusion losses increase with stack SoC. Therefore, to decrease stack SoC and lower diffusion losses, a higher flow rate during charging than during discharging is reasonable.
Ni foam supported Co3O4 nanoflakes is prepared for battery-type supercapacitor application through a simple three-step route. In briefly, Co metals are first deposited on Ni foam with a nanosheet morphology. The CoC2O4 protrudes out from the surface of Co through an in-situ reaction with H2C2O4 to form dendritic-like nanowires morphology. Finally, Co3O4 are obtained through thermal decomposition of the CoC2O4 precursor and the dendritic-like nanowires morphology is melting and transforming into a nanoflakes morphology. The unique architectures morphology with porosity and interconnected channels has great advantages since it can effectively increases the contact surface area with electrolyte, which could significantly not only enhances surface area but also the ion/electron diffusion. Electrochemical tests show that Co3O4 nanoflakes exhibit a high specific capacity up to 576.8Cg−1 at a current density of 1Ag−1 and remain 283.7Cg−1 capacity at a high current density of 50Ag−1, as well as 82% capacitance retained after 5000cycles. These above results demonstrate the great potential of Co3O4 nanoflakes in the development of battery-type supercapacitors.