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The sodium layered oxides Na2Ni2TeO6, Na2Co2TeO6 and Na1.6Sr0.2Ni2TeO6 have been synthesized by conventional solid-state method. The samples were characterized by X-ray diffractometry (XRD), cyclic voltammetry (CV), scanning electron microscopy (SEM) and charge–discharge measurements. The results show that all the samples crystallize in a hexagonal unit cell without impurity. The electrochemical Na+ extraction (i.e., the charge profile) for Na2Ni2TeO6 exhibits two voltage plateaus at 3.6 and 4.4 V, the first corresponds to Na+ ordering at extraction of 1/3 of the sodium ions per formula unit, the second to the onset of SEI formation. Detailed XPS analysis confirms that the Ni(III) does not disproportionate into Ni(III) and Ni(IV). The process of Na extraction/insertion in the interlayers of Na2Ni2TeO6 is highly reversible with a capacity of 100 mAh g−1 at slow cycling rate (0.03 C) in the 4.35 to 3 V voltage range versus Na+/Na. The lattice constant and the unit-cell volume increase with the substitution of Na+ by Sr2+. In the presence of Sr2+, the appearance of a step in the charge–discharge profile of Na1.6Sr0.2Ni2TeO6 is suppressed. Na2Co2TeO6 showed little Na extraction/insertion.
Spain is one of the major producers of broilers and laying hens in the European Union, with an overall market share of around 12%. The poultry manure that is produced is usually employed as fertilizer on cropland, either directly or after a composting process. In some cases, however, this waste is transported over 120km to be used as fertilizer, with the resulting high transport costs. In other countries, poultry manure is used as an alternative natural fuel source for power generation. In this study, poultry manure from all the laying hen farms in Asturias was characterized with a view to its possible use as an energy source. The Higher Heating Values on a dry basis (experimental) varies between 12,052 and 13,882kJ/kg. Lower Heating Values (LHVs) on a wet basis range are much lower (mean values of 2664kJ/kg) due to the high moisture content of poultry manure. Accordingly, the co-combustion of this waste with other types of waste such as forest and wood waste (LHV on a wet basis of 8044 and 15,830kJ/kg, respectively) or municipal solid waste (LHV on a wet basis of 10,725kJ/kg) should be considered as an alternative energy source. Chlorine and sulphur contents in dry matter vary around mean values of 0.64% and 0.11%, respectively. The waste also presents high amounts of Ca (4.84%) and K (2.38%).
Carbon-coated Li2ZnTi3O8 (Li2ZnTi3O8/C) anodes have been successfully synthesized using β-cyclodextrin (β-CD) as the carbon source. The effects of carbon content on the structures and physicochemical properties of the Li2ZnTi3O8/C materials are also studied in detail. It is found that the Li2ZnTi3O8 particles are nano-sized and well disperse into the carbon networks. The carbon coating greatly enhances the electrochemical performance of Li2ZnTi3O8. Li2ZnTi3O8/C-2 with the carbon content of 6.85% shows large specific capacities and good cyclic performance at high current densities. The largest capacities of 169.1, 162.4 and 150.3mAhg−1 are delivered at 3, 4 and 5Ag−1, respectively. Cycling for 100 cycles, 160.5, 139.7 and 129.1mAhg−1 are kept for the sample at the three current densities mentioned above, respectively. The good electrochemical performance of the Li2ZnTi3O8/C-2 can be attributed to the good crystallinity, proper carbon content, large pore size, small particle size and low charge-transfer resistance.
In this work, we report on the first synthesis of novel ultrathin (α-Fe2O3)1−x (V2O5) x solid-solution nanoplates via a facile one-pot hydrothermal method. Shape selection and crystallographic orientation show closely interrelated with the V2O5-modification. Irregular α-Fe2O3 particles with random exposed facets were obtained in the absence of vanadium sources. When tested as anode materials for lithium batteries, the ultrathin (α-Fe2O3)1−x (V2O5) x nanoplates show greatly enhanced performance of Li storage. Under the condition of high current density of 1C, the ultrathin (α-Fe2O3)1−x (V2O5) x nanoplates were capable of retaining a specific capacity of 771mAhg−1 over 100 cycles. Even when cycled at 5C and 10C, comparable capacities of 482 and 365mAhg−1 could be achieved, indicating an excellent rate capability.
Antimony metal nanoparticles wrapped with a-few-layer graphene coat (Sb@Gn) were fabricated from their oxide form (Sb2O3) in a micrometer dimension using a novel two-step ball-milling process. The first mechanochemical process was designed to decrease the particle size of Sb2O3 microparticles for ensuring advantages of nano size and to subsequently coat the Sb2O3 nanoparticles with a-few-layer graphene (Sb2O3@Gn). The second metallomechanical ball-milling process reduced the oxide to its metal form (Sb@Gn) by the help of Zn as a metallic reductant. The graphene layer (@Gn) blocked the alloying reaction between Sb and Zn, limiting the size of Sb particles during the metallomechanical reduction step. During reduction, oxygen species were transferred from of Sb2O3 through @Gn to Zn along redox transfer pathways rather than direct mass transfer via unsaturated vacancies in the @Gn. the redox transfer involving oxidation of @Gn by O2− is plausible routes for O2− transfer in the metallomechanical reduction. The Sb@Gn anode exhibited outstanding capacity retention along charge/discharge cycles and improved rate capability in sodium-ion batteries. The @Gn provided conductive pathways to the Sb core and limited size expansion during sodium-lithium alloying.
The effect of activated carbon (AC) surface functional groups on the cycle performance of lead-carbon batteries was studied from hydrogen evolution and nano-lead electrodeposition on the surface of the AC. AC materials were modified by oxidation methods (hot air or acid treatment) to increase acidic groups and reduction processes (alkaline treatment or heat treatment in N2) to increase alkaline groups. The surface functional groups were characterized by X-ray photoelectron spectroscopy and Boehm titration method. We used cyclic voltammetry and a three-electrode system to prepare nano-lead deposits on the surface of the AC, and studied its influence on hydrogen evolution of AC. The results show that acidic groups are beneficial to lead electrodeposition. In addition, the lead deposits with high activity covering the surface of AC could inhibit hydrogen evolution and the irreversible sulfation in lead-carbon batteries, and then result in longer cycle life under High-rate Partial-state-of-Charge conditions.
Palladium nanoparticles (PdNPs) were synthesized on Platinum (Pt) electrode by employing a potentiostatic pulse method of electrodeposition. The mechanism of electrocrystallization of PdNPs on Pt was investigated in the system containing 1mMK2PdCl4 in 0.1M H2SO4. Experimental results show that Pd electrodeposition follows the so-called Volmer–Weber growth mechanism. The electrodeposited PdNPs were characterized by X-ray photoelectron spectroscopy (XPS) and Field emmisision scanning electron microscopy (FESEM). The results obtained suggested the presence of chemisorbed oxygen on the surface of PdNPs. The influence of time of deposition on the size and monodispersity of the deposited PdNPs was investigated. The studies revealed that, the size of PdNPs increased with increase in the time of deposition. The synthesized Pd nanoparticles modified Pt electrode displayed significantly different voltammetric behavior compared to bare Pt electrode and also showed high catalytic activity towards the electrooxidation of formic acid and methanol. To the best of our knowledge, this is the first report of electrosynthesis of Pd nanoparticles using potentiostatic pulse method without using any stabilizing agent or template.
The first electrochemical investigation of transition metal borate structures are reported, focusing on FeBO3 and Fe3BO6. In Fe3BO6, uptake of lithium initiates a two-phase process that results in framework disintegration, as expected from structural considerations and formation of an amorphous material that reversibly cycles lithium with a specific capacity of 450mhA/g at an average potential of 1.6V, in the regime of anode applications. Substitution of Fe(III) with other metals in the Fe3BO6 lattice is found to be detrimental to cycling behavior. Reduction of the particle size results in a reversible capacity up to 700mAh/g, albeit with some fading on cycling.
Model based design and optimization of large scale vanadium redox flow batteries can help to decrease system costs and to increase system efficiency. System complexity, e.g. the combination of hydraulic and electric circuits requires a multi-physic modeling approach to cover all dependencies between subsystems. A Matlab/Simulink model is introduced, which covers a variable number of stacks and their hydraulic circuit, as well as the impact of shunt currents. Using analytic approaches that are afterward crosschecked with the developed model, a six-stack, 54 kW/216 kWh system is designed. With the simulation results it is demonstrated how combining stacks to strings and varying pipe diameters affects system efficiency. As cell voltage is comparatively low, connecting stacks in series to strings seems reasonable to facilitate grid connection. It is shown that this significantly lowers system efficiency. Hydraulic circuit design is varied to lower efficiency drop. In total, four different electric designs are equipped with 21 hydraulic design variations to quantify dependencies between electric and hydraulic subsystems. Furthermore, it is examined whether additional shunt current losses through stack series connection can be compensated by more efficient energy conversion systems.
This review examines the influence of the various parameters involved in the cast-on-strap (COS) process on the quality of the resulting lug–strap joints. In addition, it provides the findings of an investigation on the macroscopic and microscopic features of COS joints in commercial lead–acid batteries. Some examples of the most common defects that can affect the performance and life of batteries are presented. The nature of the fusion at the lug–strap interface for the various lugs and strap alloy compositions used in conventional, hybrid and valve-regulated lead–acid batteries are also discussed.
Numerical modelling of redox flow battery (RFB) systems for energy storage applications allows the technical performance of different designs to be predicted without costly lab, pilot and full-scale testing. A one-dimensional numerical model has been developed for RFB systems with bipolar flow-by electrodes, soluble redox couples, and recirculating batch operation. Overpotential losses were estimated from the Butler-Volmer equation, accounting for mass transfer. The effects of cross-membrane solvent transport and self-discharge were also considered. The model predicted the variation in concentration and current along the electrode and determined the charge–discharge efficiency, energy density and power density. The model was validated using data obtained from a pilot-scale bromide–polysulphide (PSB) system commercialised by Regenesys Technologies (UK) Ltd. Electrochemical rate constants were obtained by fitting the model results to the experimental data, and values of 4×10−7 and 3×10−8 ms−1 were found for the bromide and sulphide electrolytes on the activated carbon electrodes. The model was able to predict cell performance, species concentration, current distribution and electrolyte deterioration for the Regenesys system.
The aim of this study was to assess the evolution of health-related quality of Life (HRQoL), emotional burden, and neurocognitive function in the first-generation metastatic melanoma survivors treated with pembrolizumab.
The paper reviews the current state of knowledge regarding global emissions of mercury and presents a new inventory of global emissions of mercury to the atmosphere from anthropogenic sources for the year 2000. The largest emissions of Hg to the global atmosphere occur from combustion of fossil fuels, mainly coal in utility, industrial, and residential boilers. As much as two-thirds of the total emission of ca. 2190ton of Hg emitted from all anthropogenic sources worldwide in 2000 came from combustion of fossil fuels. Emissions of Hg from coal combustion are between one and two orders of magnitude higher than emissions from oil combustion, depending on the country. Various industrial processes account for additional 30% of Hg emissions from anthropogenic sources worldwide in 2000. Major contribution to emissions from this source category comes from gold production using Hg technology. The Asian countries contributed about 54% to the global Hg emission from anthropogenic sources in 2000, followed by Africa (18%) and Europe, including the European part of Russia (11%). China heads the list of the 10 countries with highest Hg emissions from anthropogenic activities. With more than 600ton of Hg, China contributes about 28% to the global emissions of mercury. It is expected that future changes of Hg emissions from anthropogenic sources worldwide until the year 2020 should be within ±20% of the current estimates, although this assessment should be treated with great caution. Emission estimates for various continents presented in this paper were used to prepare global emission maps. These maps are presented in a companion paper (Wilson et al., 2005. Spatial distribution of global anthropogenic mercury atmospheric emissions. Atmospheric Environment, in this issue).
In this work we synthesize a series of plasticizers and a crosslinker based on a multi-armed oligo(ethyleneoxy) phosphate and carry out in-situ radical polymerization of the precursor solution containing the plasticizers and crosslinker to produce semi-interpenetrating polymer network (semi-IPN) solid polymer electrolytes (SPEs). A high-quality free-standing film is obtained with a tensile strength as high as 1.2 MPa. Several factors are investigated to optimize the ionic conductivity of the solid polymer electrolytes such as the length of ethylene oxide units in the plasticizers, the concentration of lithium salts, the content of the plasticizers, and the different types of lithium salts. The maximum ionic conductivity of the SPEs is found to reach 5.0 × 10−4 S cm−1 at 30 °C, together with the wide electrochemical stability window of above 5.0 V and the columbic efficiency more than 70% in reversible lithium plating–stripping cycles, making phosphate-based semi-IPN SPEs a promising candidate for application in solid-state lithium secondary batteries.
In order to explore the local effects of electrode microstructural inhomogeneity, a half cell Li ion battery was built with reconstructed realistic LiCoO2 cathode electrode which was divided equally into eight subdomains. A previously developed C++ code was used to simulate the discharge and charge processes using finite volume method. The geometric properties of each subdomain were characterized by porosity, tortuosity and specific interfacial area. The average variables, such as Li ion concentration and reaction current density, and polarization due to different sub-processes, such as activation of electrochemical reactions (PAER) and charge transport of species were calculated in each subdomain. The inhomogeneous geometric properties result in non-uniform polarization distribution. The polarization due to ionic transport depends on the position, tortuosity and porosity. The porosity, specific interfacial area, state of discharge/charge and position play an important role in the distribution of PAER. The PAER difference between subdomains tends to enlarge at the end of discharge process but to reduce at the end of charge process although the main electrochemical reaction always takes place in the subdomains with smaller porosity. In addition, the PAER is much larger than the polarization due to ionic transport. By comparing with the results from pseudo 2D model, we found that microstructural inhomogeneity in the 3D model has significant impact on global polarization and polarization distribution in the electrode. The presented method provides a possibility to study local effect of inhomogeneous geometric properties.
Lithium–sulfur (Li–S) battery is a potential energy storage technology with high energy density and low cost. However, the gap between theoretical expectation and practical performance limits its wide implementation. Herein, we report a nitrogen-doped porous carbon derived from biomass pomelo peel as sulfur host material for Li–S batteries. The hierarchical porous architecture and the polar surface introduced by N-doping render a favorable combination of physical and chemical sulfur confinements as well as an expedite electron/ion transfer, thus contributing to a facilitated and stabilized sulfur electrochemistry. As a result, the corresponding sulfur composite electrodes exhibit an ultrahigh initial capacity of 1534.6 mAh g− 1, high coulombic efficiency over 98% upon 300 cycles, and decent rate capability up to 2 C. This work provides an economical and effective strategy for the fabrication of advanced carbonaceous sulfur host material as well as the significant improvement of Li–S battery performance.
In the field of mobile health monitoring the current most important user groups are those aged 50 +. In our project senSAVE® we developed a user interface for monitoring vital personal parameters that is specifically adapted to the needs of this group. The group is said to show less perception and control capability and has less experience in the use of information technology. More realistically, the group of 50 + users shows more diversity in their cognitive, sensory and motor skills than younger people. User interfaces for elderly people should therefore be designed for different capabilities and needs. For a mobile health monitoring system three design types were developed and evaluated in this study: three basic interfaces, two professional interfaces and an interface in between as a compromise of the two former types. Beyond monitoring the vital parameters of the user during mobile phases a stationary module for the inspection of aggregated data was included on a standard TV set together with a remote control device. The paper describes the user interface design and a comparative evaluation of the interfaces during and after the development, i.e. formative and summative evaluation. It also describes first user feedback about the stationary component.
A Li[Ni0.3Co0.4Mn0.3]O2 cathode is modified by applying a Li–La–Ti–O coating using the hydrothermal method. The coated Li[Ni0.3Co0.4Mn0.3]O2 is characterized by X-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, transmission electron microscopy, and differential scanning calorimetry. The Li–La–Ti–O coating layer is formed as crystalline (perovskite structure) or amorphous phase depending on the heating temperature. The Li–La–Ti–O coated Li[Ni0.3Co0.4Mn0.3]O2 electrode has better rate capability than the pristine electrode. In particular, the rate capability is significantly associated with heating temperature; this is probably due to the phase of the coating layer. It appears that the Li–La–Ti–O coating of amorphous phase is superior to that of crystalline phase for obtaining enhanced rate capability of the coated samples. The thermal stability and cyclic performance of the Li[Ni0.3Co0.4Mn0.3]O2 electrode are also improved by Li–La–Ti–O coating. These improvements indicate that the Li–La–Ti–O coating is effective in suppressing the chemical and structural instabilities of Li[Ni0.3Co0.4Mn0.3]O2.
The advantages of fuel cell systems on naval surface vessels are generally based on their low emissions, high comfort and high efficiency. Today the NATO-logistic fuel for naval ships is F76 marine diesel fuel. Because of its availability and the fact that the use of hydrogen onboard ships would require a much higher storage volume, the reforming of F76 diesel fuel is essential for the implementation of fuel cell systems on naval surface vessels. The DESIRE-project has been performed from 2001 until 2004 to demonstrate the feasibility of the reforming of F76 diesel fuel into a hydrogen-rich gas suitable to be utilized in PEM-fuel cells. A steam reformer system has been realized in the project. A small PEM-fuel cell has been coupled to the reformer system and operated successfully.
A simple and fast microwave-assisted protocol to functionalize commercially available graphite felts (GFs) with carbon nanofibers (CNFs) for the application as electrode materials in redox-flow batteries (RFB) is demonstrated. As catalyst for the CNF synthesis nickel acetate is applied and ethanol serves as the carbon source. By the in-situ growth of CNFs, the active surface of the electrodes is increased by a factor of 50, which is determined by the electrochemical double layer capacities of the obtained materials. Furthermore, the morphology of the CNF-coating is investigated by scanning electron microscopy. Subsequently, the functionalized electrodes are applied in a polymer-based redox-flow battery (pRFB) using a TEMPO- and a viologen polymer as active materials. Due to the increased surface area as compared to an untreated graphite felt electrode, the current rating is improved by about 45% at 80 mA cm−2 and, furthermore, a decrease in overpotentials is observed. Thus, using this microwave-assisted synthesis approach, CNF-functionalized composite electrodes are prepared with a very simple protocol suitable for real life applications and an improvement of the overall performance of the polymer-based redox-flow battery is demonstrated.
Flexible piezoelectric energy harvesters (f-PEHs) have drawn attention for their potential use as power sources for wearable electronics. However, the amount of power harvested from conventional f-PEHs is still insufficient for achieving energy autonomy; hence, they are only used for limited applications. One of the effective approaches to enhancing the energy extraction from an f-PEH is to optimize the harvesting circuits. In this article, an energy extraction enhancement circuit (EEEC) using an f-PEH based on piezoelectric (PZT) material is reported to improve energy harvesting from irregular human movement of a joint or limb. The proposed EEEC is optimized for harvesting energy from random energy inputs with varying magnitudes and intervals, just like sporadic and irregular human movement. An f-PEH with a total thickness of 170 µm is utilized, which provides sufficient flexibility for attachment on clothes or human skin. By minimizing the capacitive load experienced by the PZT material during deformation, the EEEC maximizes the output voltage and increases the amount of extracted energy with low static power consumption (1.15 nW). Compared with a conventional full bridge rectifier (FBR)-based harvesting circuit, energy extraction is enhanced up to 495%.
Halogen free flame retardant cotton (FR cotton) fabric was prepared by grafting 2,3-epoxypropyl methacrylate (GMA) on ordinary or untreated cotton (UT cotton) fabric by γ-rays from 60Co source. Epoxy groups present in GMA grafted cotton (GMA-g-cotton) fabric was reacted with ethylene diamine and subsequently modified with orthophosphoric acid solution to convert in to FR cotton fabric. Effects of imparted dose, concentration of monomer on grafting percentage were studied. The changes in thermal properties after treatment were investigated by using Thermo gravimetric analyser. Limiting oxygen index, char length, time after glow and time after flame were also studied as per ASTM D2863 and IS11871, respectively, for both FR cotton and UT cotton fabrics. The FR cotton fabric was found to pass all the above tests. Washing durability of the FR cotton fabric in different cleaning agents was also studied and a washing solution containing organic solvent mixture is suggested.