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The structural characterization and properties of lithium difluoro(oxalato)borate (LiDFOB) are reported. LiDFOB was synthesized as previously described in the literature via direct reaction of boron trifluoride diethyl etherate with lithium oxalate. The crystal structure of the salt was determined from single crystal X-ray diffraction yielding a highly symmetric orthorhombic structure (Cmcm, a =6.2623(8)Å, b =11.4366(14)Å, c =6.3002(7)Å, V =451.22(9) Å3, Z =4 at 110K). Single crystal X-ray diffraction of a dihydrate of LiDFOB yielded a monoclinic structure (P2 1 /c, a =9.5580(3)Å, b =12.7162(4)Å, c =5.4387(2)Å, V =634.63(4) Å3, Z =4 at 110K). Along with the crystal structures, additional structural information and the properties of LiDFOB (via 11B and 19F NMR, DSC, TGA and Raman spectroscopy) have been compared with those of LiBF4 and LiBOB to better understand the differences between these lithium battery electrolyte salts.
Immobilization of enzyme based on combination of adsorption and cellulose derivative membrane coating was established in this work for the first time. Laccase, a commonly used enzyme in varied fields, was chosen as the model enzyme to demonstrate this method. After investigating operational conditions, the optimal process was obtained as follows: diatomite or HPD-417 as the adsorption carrier, 0.5% (w/v) methylcellulose (40,000~50,000) acetone solution as the coating solution, 0.75% (w/v) polyethylene glycol or maltose as the protective agent, and drying at 4 °C for 9 h. Under the optimal conditions, the residual activities of diatomite and HPD-417 immobilized laccase reached 99.33% and 94.15%, respectively. The study on properties showed that the immobilized laccases held high pH tolerance and thermal stability. The immobilized laccases were further applied to the indigo decolorization and 2, 4-dichlorophenol degradation. They showed high catalytic efficiency and could be reused for several batches. On the whole, the immobilization method developed in this work can effectively avoid the inactivation of laccase during immobilization and improve the stability of immobilized laccase. The laccase immobilized by this method shows obvious potential for environmental governance.
Although it is well established that the prevalence of autism spectrum disorder (ASD) is higher in males than females, there is relatively little understanding of the underlying mechanisms and their developmental time course. Sex-specific protective or risk factors have often been invoked to explain these differences, but such factors are yet to be identified.
The redox reaction between divalent and trivalent iron species in binary and ternary molten salt systems consisting of 1-ethyl-3-methylimidazolium chloride (EMICl) with iron chlorides, FeCl2 and FeCl3, was investigated as a candidate of the half-cell reactions of novel rechargeable redox batteries based on low temperature molten salt systems. A reversible one-electron redox reaction between divalent and trivalent iron species was observed on a platinum electrode in EMICl–FeCl2–FeCl3 system at 130°C. The voltammetric data indicated that divalent and trivalent iron species were FeCl3 − and FeCl4 − complex anions, respectively. Combined with another proper redox couple, this molten salt system can be utilized in a rechargeable redox battery on account of its low melting temperature and reversible redox reaction.
The distribution system is demanded to be more efficient, more flexible and more intelligent due to the continued growth of the electricity loads, the high efficiency of energy utilization and the environmental protection. The traditional distribution systems are facing the challenge of evolving from passive networks to the active distribution networks (ADN) with the integration of multiple controllable resources. This paper presents an optimal operation and schedule model of the ADN, considering a variety of controllable resources such as distributed generations, battery storages and interruptible loads. To solve the optimization problem, a modified fuzzy adaptive PSO assisted by Kriging model (KMA-MFAPSO) is developed in this paper. In KMA-MFPSO, a novel constraint handling technique (CHT) based on the PSO is proposed to handle the constraints effectively. In addition, under the premise of ensuring the accuracy of the calculation, the Kriging model is used in KMA-MFAPSO to calculate the power flow the ADN approximately, which greatly speeds up the solving process. Finally, the effectiveness of the proposed algorithm is tested on a modified IEEE-123 system. The optimal results obtained by the proposed method are compared with the results obtained by using other solving algorithms. The simulation results indicate that KMA-MFAPSO is very robust and fast to solve the optimization problem so that it can be used in practical systems.
A number of titania films have been produced through anodising high purity titanium from different suppliers in either the as-received state or following polishing and etching. Anodising was carried out galvanostatically for a period of 10min in 0.2M H2SO4. The performance of the films was then evaluated as potential anode materials for lithium batteries. Raman spectroscopy showed these films had spectra characteristic of anatase with the presence of some rutile whilst the spectra of the lithiated state was characteristic of the orthorhombic phase of Li x TiO2. The surface condition in particular was found to have an effect on the electrochemical performance and properties of the films most notably on capacity fade. Whilst the electrodes produced from as-received titanium demonstrated stable cycle capacities after the initial few cycles, those on polished and etched substrates faded over 50cycles. The best performing films offered a capacity of at least ∼48μAhcm−2 over the 50cycles. All the electrodes examined however did show signs of the film having being damaged as a result of electrochemical cycling. With the wide range of anodising parameters that can be altered there is considerable scope for optimising the electrochemical performance of films produced through such a technique.
Concerns about climate change as well as fossil fuel usage restrictions motivate the energy transition to a sustainable energy sector requiring very high penetration level of renewable energy sources in the World energy matrix, including those heavily hydrocarbon-based as fuel for transportation. Some of these renewable sources have an uncontrollable output and managing the variability is challenging. The current upward trend in renewables participation will demand even more flexibility from the energy systems. Among several options for increasing flexibility, energy storage (ES) is a promising one considering the variability of many renewable sources. The purpose of this study is to present a comprehensive updated review of ES technologies, briefly address their applications and discuss the barriers to ES deployment. Methodology involves the description and the analysis of ES many existing and developing technologies. ES applications are discussed briefly using logistic and parametric classification logics. As result of this study, it will be pointed out that no ES technology outstands simultaneously in all technical characteristics and consequently, selection should be driven on a case base analysis. Economic feasibility of ES business models and establishment of a well-suited regulatory environment are major issues to unlock ES deployment. Regarding energy transition, Power-to-Gas, Power-to-Liquids and Solar-to-Fuel technologies are very promising and further studies about these technologies are required to better understand their possibilities and how to overcome the barriers to their practical usage.
Lithium sulfur batteries attract the increasing attentions because of the high energy density. However, sulfur cathodes suffer from several scientific and technical issues which are related to polysulfide ion migration, low conductivity, and volume changes. Many strategies such as porous hosts, polysulfide adsorbents, catalyst, and conductive fillers and so on have been proposed to address these issues, separately. In this study, novel Co3S4 nanotubes are developed to efficiently host sulfur, adsorb polysulfide, and catalyze their conversion. Because of these multifunctional advantages in one structure, the resulting Co3S4@S nanotube electrodes demonstrate superior electrochemical properties for high performance lithium sulfur batteries.
A series of samples are collected from the catholyte solution of a vanadium redox flow battery (VRFB) at different values of state of charge (SoC)/state of discharge (SoD). The samples are analyzed by means of Raman spectroscopy to identify: (i) the species present into the catholyte; and (ii) how the composition of the catholyte is modulated along the charge and discharge processes of the VRFB. Raman results reveal that the most abundant species in the catholye are VO2+ and VO2 +; they are coordinated by HSO4 − and SO4 2− ligands. During the charge process of the VRFB the equilibrium between the vanadium species is shifted towards the formation of an ensemble of V(V) complexes. Instead, during discharge a family of V(IV) species is obtained. The formation of concatenated HV2O5 − and H3V2O7 − species in the catholyte is revealed, which indicates that side electrochemical reactions occur during the charge and discharge processes of a VRFB. The presence of these side reactions plays a crucial role in the modulation of the Coulombic efficiency of the VRFB. This work highlights the complexity of the chemical situation at a VRFB cathode, and the great importance to understand/control such chemical situation to improve the performance of VRFBs in the scenario of electrochemical energy storage field.
A surface-roughened clad (S-clad) current collector significantly extends the cycle-life of the lithium ion negative electrode composed of a silicon micropowder and an aqueous binder. The high tensile strength of the S-clad is also proved to be important for improving the battery performance of the electrode by comparison to a surface-roughened pure Cu current collector. Moreover, adding 10 vol.% fluoroethylene carbonate to the electrolyte further extends the cycle-life of the Si electrode. The synergic effect of the high adhesive and tensile strength of the S-clad current collector as well as the electrolyte additive results in maintaining the reversible capacity of 1000 mA h g−1 for more than 1000 cycles, in which 1.0–1.2 mg cm−2 of the active material is loaded on the electrode.
The Li4Ti5O12/C composite with lump morphology and excellent rate performance are synthesized using a facile hydrothermal method followed by a low temperature heat treatment. In the hydrothermal process, the introduction of cetyltrimethylammonium bromide (CTAB) as a surfactant significantly improves the rate performance of Li4Ti5O12/C composite as anode material for lithium ion battery (LIB). The specific capacities of the obtained composite at charge and discharge rates of 0.1, 1, 5, 10 and 20 C are 176, 163, 156, 151 and 136 mA h g−1, respectively, which is apparently larger than those of the Li4Ti5O12/C free from CTAB in the preparation. The Li4Ti5O12/C prepared in presence of CTAB also shows excellent cycling performance at high rate, which is attributed to its larger diffusion coefficient of lithium ion (6.82 × 10−12 cm2 s−1) and smaller charge-transfer resistance (Rct) (19.2 Ω) than those of the composite (1.22 × 10−13 cm2 s−1 and 50.2 Ω) free from CTAB in the preparation. The Li4Ti5O12 particles obtained in presence of CTAB are coated uniformly by a thin carbon layer with a thickness of ∼1 nm, whereas the Li4Ti5O12 particles obtained in absence of CTAB are covered by relatively thick surface layers with a thickness of ∼2.5 nm, which is too thick, blocks the lithium ion diffusion and leads to low ionic conductivity.
The discharge performance of the wrought Mg-3Al-1Zn (AZ31), Mg-8Li-3Al-1Zn-0.2Y (LAZ831), and Mg-11Li-3Al-1Zn-0.2Y (LAZ1131) anodes (wt.%) for Mg-air primary batteries is investigated using an aqueous electrolyte (3.5 w% NaCl-solution). The AZ31, LAZ831 and LAZ1131 anodes are mainly composed of the equiaxed α-Mg (hcp) grains, the α-Mg (hcp) + β-Li (bcc) fibers, and the single β-Li (bcc) phase, respectively. The phase constitution has a strong influence on the discharge performance of Mg based anodes. The active β-Li phase provides high and stable cell voltage. Furthermore, the fine and dense active particles in the matrix contribute to a uniform corrosion and good corrosion resistance. In addition, the active β-Li peels away in the form of particle clusters. The LAZ1131 anode has the best discharge performance at a large current density of 40 mA cm−2. The highest discharge capacity and anodic efficiency are 1478 mAh·g−1 and 62.1%, respectively. It suggests that the LAZ1131 anode is a good excellent candidate for high performance Mg-air batteries.
Making efficient trifunctional non-precious metal catalysts for simultaneously catalyzing oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in same electrolyte is very important to bring energy conversion and storage systems into realities. Herein, hierarchical Co9S8 hollow microspheres had been designed and synthesized by a facile hydrothermal reaction at 140°C (denoted as Co9S8 HMs-140). The properties and formation process of the Co9S8 HMs-140 were systematically investigated. Owing to the composition and structure features, the Co9S8 HMs-140 can be used as a trifunctional catalyst for ORR, OER and HER in the same alkaline electrolyte. The Co9S8 HMs-140 shows reasonable ORR and HER performance. Additionally, OER performance of the Co9S8 HMs-140 is superior to that of RuO2, such as a low onset potential (1.47V vs. RHE) and high stability. Furthermore, due to the bifunctional OER and HER activity of the Co9S8 HMs-140, the Co9S8 HMs-140 affords an O2 efficiency of 31 mmolh−1 and a H2 efficiency of 62mmolh−1 at 1.60V in 1M KOH solution under the given time range, exhibiting a 96% faradaic yield in the process of full water splitting to produce O2 and H2. The present work will provide a promising prospect for the development of multifunctional transition metal sulfides as effective electrocatalysts for sustainable energy systems.
In recent decades, typical and pathologic behavioral and mental aging in family dogs has received increased attention. This article reviews the literature and highlights methodological inconsistences in this field. Most methodological concerns originate from disregarding the interaction of proximate and ultimate causes of this phenomenon. The literature review revealed several studies on family dogs that lack the methodological rigor needed for establishing a well-defined phenotype. The main issues include the chronological threshold accepted for aged dogs, the phenotypical features regarded as pathologic and the method applied to validate different behavioral scales. In addition, no baseline has been established for many studied behavioral and mental features by analyzing healthy adult population of dogs. In family or pet dog samples, the difference in the life expectancy of dog breeds is rarely taken into account, so it is not clear whether the observed changes are due to the normal aging process or are signs of an accelerated decline (senile dementia). We suggest that questionnaire studies should be complemented by behavior test batteries to validate data obtained from owners, and more attention should be given to the composition of the populations involved in the research. An effort should be made to discriminate normal or typical and pathologic aging in future work. Only by adopting a more rigorous approach can we identify risk and protective factors in dogs and reveal the aspects in which the family dog can provide a good animal model for human aging.
Lithium-sulfur (Li-S) batteries attract much attention due to its high specific capacity and energy density compared to lithium-ion batteries (LiBs). Herein, a novel composite named as (void/nano-Li4Ti5O12 pieces)@C [(v/n-L)@C] was designed and prepared as a sulfur host. Spinel Li4Ti5O12 here as a multifunctional additive played as polysulfide adsorbent agent and fast Li+ conductor, and carbon shell was designed as electronic conductor, as well as volume barrier to limit the volume expansion caused by sulfur. As-prepared (S/nano-Li4Ti5O12 pieces)@C [(S/n-L)@C] are core-shell spheres, which are about 200 nm in size. Nano-Li4Ti5O12 and sulfur were coated by the outer carbon shell with a thickness of about 20 nm. The experimental results show that electrochemical performances of (S/n-L)@C cathode were enhanced effectively compared to S@C cathode. At 0.5C and 1C, the discharge capacity of (S/n-L)@C was 33.5% and 40.1% higher than that of S@C at 500th cycle. Even at 2C, its capacity reached 600.9 mAh g−1 at 1000th cycle. Li+ conductivity of (S/n-L)@C was one order of magnitude higher than that of S@C, which was reach to 2.55 × 10−8 S cm−1. The experiment results indicate Li4Ti5O12 plays a promotional role on electrochemical performances of sulfur cathode, especially for stable cycling performance and high rate performance.
Fuel cell vehicles (FCVs) running on hydrogen do not cause local air pollution. Depending on the energy sources used to produce the hydrogen they may also reduce greenhouse gases in the long term. Besides problems related to the necessary investments into hydrogen infrastructure, there is a general notion that current fuel cell costs are too high to be competitive with conventional engines. But given historical evidence from many other technologies it is highly likely that learning by doing (LBD) would lead to substantial cost reductions. In this study, we implement potential cost reductions from LBD into an existing agent-based model that captures the main dynamics of the introduction of the new technology together with hydrogen infrastructure build-up. Assumptions about the learning rate turn out to have a critical impact on the projected diffusion of the FCVs. Moreover, LBD could imply a substantial first mover advantage. We also address the impact of learning spillovers between producers and find that a government might face a policy trade-off between fostering diffusion by facilitating learning spillovers and protecting the relative advantage of a national technological leader.
Rheumatoid arthritis is characterized by the presence of circulating auto-antibodies, including rheumatoid factors, which recognize the Fc portion of IgGs. The neutrophil is the most abundant circulating leukocyte and it expresses high levels of FcγRs on its surface. The aim of the present study was to examine the capacity of circulating human neutrophils to be activated by rheumatoid factors and the consequences of these events on endothelium.
This paper deals with the application of lithium ion polymer batteries as electric energy storage systems for hydrogen fuel cell power trains. The experimental study was firstly effected in steady state conditions, to evidence the basic features of these systems in view of their application in the automotive field, in particular charge–discharge experiments were carried at different rates (varying the current between 8 and 100A). A comparison with conventional lead acid batteries evidenced the superior features of lithium systems in terms of both higher discharge rate capability and minor resistance in charge mode. Dynamic experiments were carried out on the overall power train equipped with PEM fuel cell stack (2kW) and lithium batteries (47.5V, 40Ah) on the European R47 driving cycle. The usage of lithium ion polymer batteries permitted to follow the high dynamic requirement of this cycle in hard hybrid configuration, with a hydrogen consumption reduction of about 6% with respect to the same power train equipped with lead acid batteries.
In this work, spinel LiNi0.5Mn1.5O4 (LNMO) hollow microspheres are synthesized by an impregnation method using microsphere MnO2 as both the precursor and template. To enhance the electrical conductivity of LNMO, metal Al was employed for the first time as a coating material for LNMO. Though an Electron-beam Vapor Deposition approach, the surface of LNMO can be easily coated by a tight layer of Al nanoparticles with adjusted thickness. Further annealing the Al-coated sample at 800°C in air, the Al3+-doped LNMO can be obtained. The effects of Al-coating and Al3+-doping on the sample morphology and structure are investigated by SEM, TEM, XRD and FT-IR. The electrochemical properties of Al-coated LNMO and Al3+-doped LNMO are measured with comparison of bare LNMO by charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results show that both Al-coating and Al3+-doping can greatly enhance the cycle performance and rate capability of LNMO. Especially for Al-coated LNMO, it shows the lowest battery impedance due to the existence of conductive Al coating layer, thus delivers the best rate performance among the three. The physical coating procedure used in this work may provide a new facile modification approach for other cathode materials.
As utility electricity rates evolve, pairing solar photovoltaic (PV) systems with battery storage has potential to ensure the value proposition of residential solar by mitigating economic uncertainty. In addition to batteries, load control technologies can reshape customer load profiles to optimize PV system use. The combination of PV, energy storage, and load control provides an integrated approach to PV deployment, which we call “solar plus”. The U.S. National Renewable Energy Laboratory’s Renewable Energy Optimization (REopt) model is utilized to evaluate cost-optimal technology selection, sizing, and dispatch in residential buildings under a variety of rate structures and locations. The REopt model is extended to include a controllable or “smart” domestic hot water heater model and smart air conditioner model. We find that the solar plus approach improves end user economics across a variety of rate structures – especially those that are challenging for PV – including lower grid export rates, non-coincident time-of-use structures, and demand charges.
Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10−4 S cm−1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g−1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.