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Understanding the degradation factors (cathode and anode degradation and solid electrolyte interface (SEI) formation) of lithium-ion batteries (LIBs) with a blended cathode is necessary to improve their durability because battery drive vehicles often use LIBs with a blended cathode due to advantages of power and cost. We developed a dV/dQ curve analysis adapted for through a dQ/dV curve analysis to elucidate the relations between cycle test conditions and degradation factors. To compare said factors, cycle tests were conducted under different conditions: one charge/discharge rate (C/3), two state-of-charge (SoC) ranges (100%–0% and 100%–70%), and three temperatures (0 °C, 25 °C, and 45 °C). We confirmed that there are clear differences in the degree of contribution of each degradation factor depending on conditions. For instance, at 0 °C, although the capacity reduction rate was almost the same regardless of the SoC range, the degradation mechanisms were different, i.e., the cathode degradation and the SEI formation occurred at the same time, resulting in the reduced capacity for the 100%–0% SoC range, while capacity reduction was mainly due to SEI formation for the 100%–70% SoC range.
Publisher Summary This chapter describes the different aspects of tunas in captivity. There are tuna ranches or farms throughout the Mediterranean Sea, Japan, Australia, and Mexico. All three bluefin tuna species are currently involved in farming operations. The collection of tuna for the farming operations in the Mediterranean area, Mexico, and Australia rely primarily on tuna caught by purse seine. The seined tuna are transferred to a tow-pen, which is approximately 45 m in diameter and 15 m deep. In Japan, Pacific bluefin tuna, Thunnus orientalis, are collected from the Shikoku and Kyushu islands by commercial fisherman, trolling small-feathered lures along the edge of the Kuroshio Current. The live tuna are held in onboard tanks with running seawater and are then transported back to the tuna farms, where they are transferred to large rectangular pens, measuring 24 by 50 m and 15 m deep. Bluefin tuna are more challenging to collect and require the use of standard rod and reel sportfishing techniques, using baited barbless hooks. Bluefin behavior differs from yellowfin in that they rarely bite on liftpole lure, which necessitates using standard rod and reel sportfishing tackle. It is found that the feeding regime of tunas is calculated according to the biomass of fishes.
Amorphous Sn2P2O7 thin film electrodes have been successfully fabricated by radio frequency (r.f.) magnetron sputtering. Reversible lithiation and delithiation processes occurring at 1.47V and 2.01V versus lithium are observed in both discharge/charge curves and cyclic voltammograms of the amorphous Sn2P2O7 thin film electrodes for the first time. Large reversible capacity around 887mAhg−1 is achieved when the cell is cycled between 0.01V and 4.0V, corresponding to 9.2 Li per Sn2P2O7 unit. Based on X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) evidences, the reaction mechanism involving the reversible decomposition and regeneration of amorphous Sn2P2O7 as well as alloying and de-alloying of tin with lithium is proposed.
In this work, we report the preparation and properties of Au-based cavity-microelectrodes. The use of gold as cavity current collector allows obtaining a regular cylindrical recess, whose volume is easily determined with good accuracy and precision. This in turn leads to an improved and much more reliable use of the cavity microelectrode (C-ME) as a tool for the quantitative characterization of finely dispersed materials and for their quantitative rapid screening. The features of Au/C-MEs are well demonstrated by the good linear correlation between the cavity volume (determined by electrochemical methods) and the quantity of charge related to the amount of electroactive powder inserted into the cavity. To prove this point, we adopted two different test systems: Pt/C and an IrO2-based material. Finally, we proved the adequacy of Au/C-MEs in the case of Ag particles as electrocatalysts for the hydrodehalogenation of trichloromethane. In this last part, C-ME interestingly appears as a flexible and versatile tool that presents peculiar features: the voltammetric signal can be controlled by either the electron transfer or by mass transport and can be associated to the outer surface or to the whole amount of material inserted into the cavity. This means that C-MEs can be used either as a microdisk of a desired material (that is very useful, especially in scanning electrochemical microscopy) or for precise quantitative studies of the material inserted inside it.
Direct internal pressure measurements of the cylindrical Li-ion cells with a mixture of LiCoO2 and Li1.167Ni0.233Co0.1Mn0.467Mo0.033O2 (a solid solution between 0.4 Li2Mn0.8Ni0.1Mo0.1O3 and 0.6 LiNi0.4Co0.2Mn0.4O2) as cathode and graphite as anode have been performed during cell charging. Cell internal pressure at the end of charging is greatly reduced from 2.85 to 0.84–1.84 bar by adding a small amount of phosphorus derivatives such as triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), and triethyl phosphite (TEP) into a carbonate-based electrolyte. The phosphorus derivatives are supposed to react with O2 generated from the decomposition of the Li2MnO3 component. The chemical states of additive molecules before and after the charging process have been characterized with a nuclear magnetic resonance (NMR) spectroscopy and gas chromatography–mass spectrometry (GC–MS). It has also been shown that those additives improve the cycle life when applied in coin full cells.
Synthesis and characterization of LiNi x Co1−2x Mn x O2 (1/3≤ x ≤1/2) electrode powders prepared by a sol–gel method were investigated. The synthesized LiNi x Co1−2x Mn x O2 materials with single phase and R 3 ¯ m layered structure were confirmed from X-ray diffraction analysis. The particle size distribution of the materials synthesized by the sol–gel process is quite uniform. Increasing the x value in the synthesized LiNi x Co1−2x Mn x O2 powder leads to decrease its particle size and increase its cation mixing. The average particle size for the LiNi0.375Co0.25Mn0.375O2 powder was found to be an order of 0.3–0.4μm. The best specific capacity of 192mAhg−1 was obtained for the LiNi0.375Co0.25Mn0.375O2 electrode with good capacity retention among the synthesized materials cycled at 0.1C in the potential between 3.0 and 4.5V at room temperature. Although structural parameters of the LiNi0.375Co0.25Mn0.375O2 powder are similar to those of the LiNi1/3Co1/3Mn1/3O2 powder, its specific capacity is higher due to the increase of the stoichiometry of active site Ni. The increase of Ni and Mn content could reduce cost of the materials. It was found that the cell performance of the LiNi x Co1−2x Mn x O2 electrode drops dramatically and its cation mixing increases while the x value is higher than 0.4.
In this work, the electrochemical activity of carbon felt (CF) for the V2+/V3+ redox reaction is improved by combining KOH-etched pretreatment with uniform Bi nanoparticles deposition. CF is functionalized by the KOH activated pretreatment, resulting in micropores structure on the surface and an increase of oxygen-containing functional groups up to 16.49%. The micropores structure and high content of oxygen-containing functional groups of KOH-etched carbon felt (CFE) promote the uniform distribution of Bi nanoparticles on the surface of CFE with an average particle size of 45nm. The resulting carbon felt (CFE-Bi) significantly enhances the electrochemical activity for V2+/V3+ redox couple because of the synergistic catalysis between the CFE and the Bi nanoparticles. The peak potential separation (ΔEp) and the charge transfer resistance of CFE-Bi is 182mV and 0.160Ω cm2, which are much lower than that of CF (427mV and 3.238Ω cm2) under the same conditions. Moreover, the energy efficiency of VRFB based on the CFE-Bi as negative electrode achieves 79.3% at 160mAcm−2, which is 36.2% higher than that of the VRFB with raw carbon felt. Overall, CFE-Bi is a promising electrode for the V2+/V3+ redox couple reaction in VRFB.
Over their designed lifetime, high-temperature electrochemical devices, such as solid oxide fuel cells (SOFCs), can experience degradation in their electrochemical performance due to environmental conditions, operating conditions, contaminants, and other factors. Understanding the different degradation mechanisms in SOFCs and other electrochemical devices is essential to reducing performance degradation and increasing the lifetimes of these devices. In this paper, SOFC degradation mechanisms are evaluated, and a damage model is presented that describes performance degradation in SOFCs due to damage or degradation in the SOFC electrodes. A degradation classification scheme is presented, dividing the various SOFC electrode degradation mechanisms into categories based on their physical effects on the SOFC. The damage model and classification method are applied both to sulfur poisoning and antimony poisoning, which occur in the SOFC anode. For sulfur poisoning, the model can calculate degradation in SOFC performance based on the operating temperature of the fuel cell and the concentration of gaseous sulfur species in the anode. For antimony poisoning, the effects of nickel consumption from the anode matrix are investigated.
The current international interest in well-being indicators among governmental agencies means that many quality of life scales are potential components of such national indicator sets. Measuring well-being in minority groups is complex and challenging. Scales are available that have been validated in specific parts of the population, such as older people. However, validation among combinations of minority groups, such as older adults of ethnic minority backgrounds, is lacking.
Iron oxide/carbon nanofibers (FeOx/CNFs) were prepared by electrospinning FeCl3·6H2O-polyacrylonitrile (PAN) precursors and heat treating at 400, 600, 800, 1000°C. As carbonization temperature increased, granular FeOx gradually migrated from nanofiber interior with effectual contacts between electrolyte and active materials rising at first and then falling; Oxidation states of iron in FeOx/CNFs changed from Fe2O3 to FeO and Fe with an improvement of capacity retention and an extra reversible capacity catalyzed by Fe; Graphitization process of carbon matrices proceed with less defective structures and heteroatom contents, leading to an increase of conductivity and a diminution of irreversible reactions during cycling. As systematically studied and compared in electrochemical performance, FeOx/CNFs with FeO, Fe state, highly graphitized carbon matrices and migration structure with FeO and Fe both embedded in and dispersed on carbon matrices presented stable cycling performance with a reversible capacity of ∼674 mAhg−1 after 60 cycles and outstanding rate capability. The above trade-off study of all the cooperative factors that affected the electrochemical property might make an effective guidance for preparation of promising FeOx/CNF anodes.
The preparation and characterization of Pb1-x Ba x Li2Ti6O14 (x = 0, 1/4, 1/2, 3/4, 1) as anode materials for lithium ion batteries are investigated in this research. The structure, morphology and electrochemical properties are compared with each other by changing the Pb/Ba atomic ratio in Pb1-x Ba x Li2Ti6O14. It can be observed that each sample shows the same orthorhombic structure with Cmca space group. Moreover, it can also be found that the working potential, conductivity, cycling and rate performances of as-received samples gradually change along with the evolution of x in Pb1-x Ba x Li2Ti6O14 (x = 0, 1/4, 1/2, 3/4, 1). Electrochemical evaluation shows that the operating potential of the as-received sample gradually decreases with increasing x value in Pb1-x Ba x Li2Ti6O14 and its initial charge capacity increases reversely. Moreover, different Pb/Ba atomic ratio also brings different cycling stability for Pb1-x Ba x Li2Ti6O14. Especially for Pb3/4Ba1/4Li2Ti6O14, it presents better electrochemical properties than other samples. After 120 cycles, the reversible capacity of Pb3/4Ba1/4Li2Ti6O14 is maintained at 129.7 mAh g−1 with capacity retention of 88.3%. In addition, its electrochemical reversibility is also demonstrated by in-situ X-ray investigation.
Lightweight tactile sensor with multimodal capabilities such as, wearability, self-powered operation, and mechanical robustness are of paramount importance in emerging portable electronics that involves human–machine integration. In this effort, an all-fiber wearable nanogenerator (NG) is designed, where, platinum (Pt) nano-particles (NPs) interfaced highly aligned 1D poly(vinylidene fluoride) (PVDF) nano-fibers arrays (Pt-PVDF NFs) is sandwiched between flexible conducting fabrics, consisting of interlocking micro-fibers arrays. In-situ ternary synergistic enhancement of piezoelectricity in nano-dimensionally confined 1D Pt-PVDF NFs arises from extensional force exertion on electrified solution jets, mechanical stretching on rapid collection and Pt-NPs interfacing with macromolecular PVDF chain. As a consequence, mechanically robust structure of Pt-PVDF NFs possess 5 times enhanced piezoelectric figure of merit ( FoM p ≈ 5 × 10 − 11 Pa − 1 ) in comparison to pure PVDF nano-fibers ( FoM p ≈ 9.7 × 10 − 12 Pa − 1 ). In addition, owing to the geometrical stress confinement effect, the Pt-PVDF NFs based piezoelectric nanogenerator (PtPENG) is proven to be a high-performance (output voltage, Voc~ 30 V and current, Isc~ 6 mA cm−2) and durable (~ 90,000 cycles) power generating device (output power, 22 µW cm−2) for small power consumer electronics. Importantly, PtPENG is demonstrated as a static strain-sensitive wearable tactile sensor that paves the way to improve human personalized healthcare monitoring system.
Background The number of drivers over 65years of age continues to increase. Although neck rotation range has been identified as a factor associated with self-reported crash history in older drivers, it was not consistently reported as indicators of older driver performance or crashes across previous studies. It is likely that drivers use neck and trunk rotation when driving, and therefore the functional range of motion (ROM) (i.e. overall rotation used during a task) of older drivers should be further examined. Objective Evaluate older driver performance in an immersive virtual reality, simulated, dynamic driving blind spot target detection task. Methods A cross-sectional laboratory study recruited twenty-six licensed drivers (14 young between 18 and 35years, and 12 older between 65 to 75years) from the local community. Participants were asked to detect targets by performing blind spot check movements while neck and trunk rotation was tracked. Functional ROM, target detection success, and time to detection were analyzed. Results In addition to neck rotation, older and younger drivers on average rotated their trunks 9.96°and 18.04°, respectively. The younger drivers generally demonstrated 15.6° greater functional ROM (p <.001), were nearly twice as successful in target detection due to target location (p =.008), and had 0.46s less target detection time (p =.016) than the older drivers. Conclusion Assessing older driver functional ROM may provide more comprehensive assessment of driving ability than neck ROM. Target detection success and time to detection may also be part of the aging process as these measures differed between driver groups.
A two-step approach for state-of-health (SOH) estimation of a lithium-ion (Li-ion) battery is developed. In the first step, state-of-charge (SOC) estimation is performed by a constrained extended Kalman filter (EKF) based on the so-called equivalent-hydraulic model. The latter model allows to characterize the internal battery state and main physical parameters while being suitable for on-line computation. The internal battery states are further exploited in the second step of the approach to obtain parameter-based SOH indicators that characterize the long term evolution of the diffusion and charge transfer processes associated to aging. Capacity and power fade indicators are determined by using notably an instrumental variable method in order to obtain unbiased parameter estimates in the presence of heteroscedastic colored noise. The methodology is validated on both simulation and experimental data for a lithium iron phosphate (LFP) half battery cell. This also provides insight on the properties of the LFP electrodes.
Electrochemical characteristics of the electrical double layer capacitor based on the nanoporous vanadium carbide derived carbon electrodes in 1M (C2H5)3CH3NBF4 acetonitrile solution have been studied using cyclic voltammetry, constant current charge/discharge and electrochemical impedance spectroscopy methods. The dependence of ideal polarizability limits, time constant, complex power components, gravimetric capacitance and other parameters of carbons prepared at different chlorination temperatures have been obtained. The gas adsorption measurements have been used for determination of the specific surface area, pore size distribution, micropore volume and other characteristics, noticeably depending on the carbon material synthesis temperature.
This study involves the design and investigation of a low-frequency, broadband, tri-hybrid energy harvester. The harvester consists of a novel septuple-stable nonlinearity-enhanced mechanical frequency up-conversion mechanism that not only enhances the output performance of the frequency up-conversion via inter-well motions, and also offers a wide and highly efficient operating bandwidth at low acceleration via the combination of resonant inter-well oscillation behavior and non-resonant behavior. The integration of an impact-driven piezoelectric generator, an electromagnetic generator, and a freestanding-mode triboelectric nanogenerator allows more energy to be harvested from a single mechanical motion, which further improves the power density. A prototype is fabricated and demonstrated using an electrodynamic shaker and various human motions. In the electrodynamic shaker test, the prototype exhibits a broad bandwidth of 2–12.5 Hz and generates an output power of 24.17 mW, corresponding to a power density of 700.3 W/m3 across a matching load resistance of 35 kΩ at a frequency of 5 Hz and 1 g acceleration. Under various basic human motions such as handshaking, walking, and slow running, the prototype can generate output powers of 38.5, 24.5, and 27.2 mW, respectively, in horizontal positions and 42.7, 10.2, and 33.1 mW, respectively, in vertical positions. A comparison study is also presented to demonstrate that the tri-hybrid prototype can produce a much higher power density than other devices reported recently. This work makes significant progress toward hybrid-energy harvesting from various human motions and its potential application in powering wearable devices.
The electrodeposition of zinc has been studied in the rotating cylinder Hull (RCH) cell with continuous and pulse interrupt current as one of the half-cell reactions for a zinc/air redox flow battery. The morphology of all pulse current deposits was discussed on the basis of the practical current density distribution. The experiments were performed in additive-free 8M potassium hydroxide electrolytes at 60°C, electrolyte flow velocities of 3, 6 and 16cms−1, and zincate concentrations of 0.2 and 0.5 M. In contrast to continuous current deposition, compact zinc deposits have been obtained in Rota-Hull experiments with pulse interrupt current at all electrolyte flow velocities and zincate concentrations. The non-compact filamentous mossy morphology, predominant in continuous current deposition, was not observed. For the highest practical current densities, current efficiencies between 96 and 100% have been found in pulse current experiments. The local practical current densities of all pulse and one continuous current depositions could be determined from the thickness of the zinc deposits measured by X-ray fluorescence. Under the most critical conditions for the deposition of compact zinc, i.e. low zincate concentrations of 0.2M and low electrolyte flow velocities of 3cms−1, pulse interrupt current produced compact zinc deposits up to the limiting current. The results of the pulse current electrodepositions are explained on the basis of the ratio of applied pulse current density to limiting pulse current density. The limiting currents in the Rota-Hull cell were calculated with zincate diffusion coefficients of 6.09×10−6 cm2 s−1 (0.2M zincate) and 6.38×10−6 cm2 s−1 (0.5M zincate) determined by rotating disc electrode experiments at 60°C. The absence of the filamentous mossy zinc morphology in pulse interrupt current experiments is ascribed to an effect of the off-time.
The development of highly effective and low-cost non-noble metal electrochemical catalysts for oxygen evolution reactions (OER) is a major challenge for overall water splitting and rechargeable metal-air batteries. In this study, we develop a novel hollow cobalt-borate modified cobalt oxide composite (denoted by Co-B-O@Co3O4) catalyst derived from zeolitic imidazolate framework-67 (ZIF-67) for electrochemical OER. The Co-B-O@Co3O4 was easily synthesized via pyrolysis of ZIF-67 in Ar and air to produce hollow Co3O4 (denoted by h-Co3O4), followed by simple NaBH4 treatment at ambient temperature for 4 h. The unique polyhedral morphology was well preserved during the NaBH4 treatment. Benefiting from its structural and compositional merit, the as-synthesized Co-B-O@Co3O4 exhibit excellent electrocatalytic activity and long-term stability for OER. Also, we conducted the OER test using a Co-B-O@Co3O4 catalyst in a neutral pH environment for further investigation. Our study can provide an insight into catalyst modification step to enhance the overall performance while keeping its physical structure simultaneously. using metal-organic framework for the electrochemical catalyst thus can be recognized as a method for producing a highly active, long-term working and novel engineered electrocatalyst for OER applications.
Aligned carbon nanotube (ACNT)/MnO2 nanocomposites were fabricated using the reduction between potassium permanganate and ACNT under the microwave irradiation. Due to good contact between ACNT and current collector during the charge/discharge process, compressible ACNT/MnO2 nanocomposites show better electrochemical properties compared to pure MnO2 and ACNT, such as high specific capacitance, good rate performance and cycling stability (2.7% loss of the initial value after 3000 cycles). These results demonstrate that ACNT/MnO2 nanocomposites have potential application for supercapacitors as high-rate electrode materials.
A novel dot matrix and sloping baffle flow field plate for proton exchange membrane fuel cell (PEMFC) cathode is designed. The plate consists of dispersive and arrayed blocks with sloping angles as shoulders. Features of the plate include a large fluid domain, and air guidance in two directions is achieved by sloping sides of the block. The cell output performance, internal transport process and liquid water removal process of the PEMFC with the matrix flow field are numerically investigated by three-dimensional two-phase full cell model and volume of fluid (VOF) model. The simulation results show that compared with the parallel and serpentine flow field, the matrix flow field can achieve high cell output performance by both improving oxygen supply to gas diffusion layer (GDL) and uniform distribution. Comparing five matrix flow fields with different block sizes and numbers shows that adequate contact area between the plate and GDL for current conductor is critical. For liquid water removal process in the matrix flow field, liquid water is hardly blocked by arrayed blocks and can leave GDL quickly. In summary, the matrix flow field fits high current density demand of PEMFC well, and some new perspectives on flow field design are presented.