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This work employs a novel technique in which laponite clay-modified gold electrodes are used as the anode for direct methanol fuel cells. The platinum/laponite clay (Pt/Clay) films on indium tin oxide electrode were characterized by using scanning electron microscope and energy-dispersive X-ray spectroscopy. Various contents of laponite clay (0.1, 0.5, 1.0, and 2.0 wt%) with constant platinum (Pt) catalyst content on modified gold electrodes were studied as an anode catalyst for methanol oxidation. The catalyst poisoning was observed as a function of time. The 1.0 wt% Pt/Clay-modified gold electrode shows the highest activity for methanol oxidation, 27.73 % higher than Pt only modified gold electrode at 2.5 min. The peak current of 1 % Pt/Clay-modified gold electrode is 3.50 % higher than the peak current of Pt only modified gold electrode at 57.5 min. The higher content of Pt/Clay-modified gold electrode shows strong resistance to catalyst poisoning. The Pt/Clay-modified gold electrode is a new and promising electrode for a direct methanol fuel cell and can replace existing commercial catalysts.
Cobalt (Co) nanoparticles anchored porous N-doped carbon nanosheets (Co@PNCS) were fabricated using a facile one-pot pyrolysis route and tested as high-performance cathode catalysts for Li-O2 batteries. The hierarchical structure was made of cobalt nanoparticles distributed in the crumpled porous carbon nanosheets. Uniformly distributed and exposed cobalt nanoparticles in the PNCS exhibited a higher electrocatalytic activity compared to Co nanoparticles anchored nitrogen-carbon materials (Co-N-C). Density function theory (DFT) calculations based on the interfacial model demonstrated that the active Co sites exhibited a more stable binding ability to discharge Li2O2 products than that of the active N sites, and Li2O2 could be reversibly formed and decomposed during cycling. Owing to optimal loadings of Co nanoparticles (16.03 wt%), the Co@PNCS-2 cathode exhibited a high specific capacity of 11,329 mAh g−1 and extended cycling life of 120 cycles, highlighting the great potential as cathode catalysts for Li-O2 batteries.
A facile scalable strategy is reported for the synthesis of a hybrid of lithium titanate (Li4Ti5O12 or LTO) and 1-pyrenecarboxylic acid decorated multiwalled carbon nanotubes (PCA@CNTs). LTO platelets comprising of quasi-spherical nanoparticles afford short diffusion paths for electrolyte ions. PCA@CNTs, enhance the electrical conductivity of the nearly insulating LTO by 3 orders of magnitude, thus maximizing the ion-uptake capability of the hybrid. Symmetric and asymmetric supercapacitors with the LTO/PCA@CNTs hybrid supported over Ni foam substrates are assembled with a novel Li+ conducting alginate gel, in air without any inert conditions that are typically used for all LTO based devices. The gel shows an average ionic conductivity of ∼8.4 mS cm−1 at room temperature, and is found to be electrochemically stable over a wide operational voltage window of ∼2.5 V. Benefitting from the synergy of electrical double layer (EDL) storage afforded by PCA@CNTs, ion-storage by LTO through a redox reaction and EDL, and the ease ion-movement across the cell due to the open architecture of CNTs, the asymmetric LTO/PCA@CNTs hybrid cell outperforms the symmetric cells by a large margin. The best areal specific capacitance (SC), volumetric SC and energy density are ∼54 mF cm−2, ∼4.3 F cm−3 (at 0.5 mA cm−2) and ∼3.7 mWh cm−3 (at a power density of 49.6 mW cm−3) significantly enhanced for the asymmetric LTO/PCA@CNTs hybrid cell, compared to the symmetric- PCA@CNTs and hybrid cells. The design is simple to implement and can serve as a prototype to develop a range of yet unexplored LTO/carbon nanomaterial based supercapacitors.
Novel porous NiO hollow microspheres are fabricated by a facile two-step method involving the ultrasound-assisted synthesis of nickel oxalate precursors and subsequent thermal annealing in air. The as-prepared NiO microspheres are composed of loosely packed nanoparticles with diameters around 30–80nm, and have a main pore distribution from 3 to 20nm with a mean pore size of 5.7nm. When evaluated as anode material for lithium ion battery, the porous NiO hollow microspheres showed enhanced electrochemical performance with high lithium storage capacity, satisfactory cyclability and rate capacity. The reversible capacity of the NiO microspheres retained 380mAhg−1 after 30 cycles at 200mAg−1. Even when cycled at various rate for more than 60 cycles, the capacity could recover to 520mAhg−1 for the current of 100mAg−1. The good lithium-storage performance can be attributed to the unique porous architecture, which provides the structural flexibility for volume change and the routes for fast Li+ diffusion.
Spinel LiNi0.5Mn1.5O4 (Fd-3m) powders are synthesized by a facile one-step sol-gel approach with a resorcinol formaldehyde (RF) resin as a chelating agent. The cross-linked metal-containing RF xerogel particles are sintered at different high temperatures from 750 to 950°C to produce several micron-sized LiNi0.5Mn1.5O4 powders. Electrochemical measurements suggest that the 850°C-sintered (in air) sample (Fd-3m phase) performs the best with a discharge capacity of 141 mAh g−1 at 0.1C and 110 mAh g−1 at 10C, and capacity-retention of 96.3% after 60 cycles at 0.25C and 89% after 200 cycles at 1C. For comparison, the LiNi0.5Mn1.5O4 sample sintered at 850°C in O2 (P4332 phase) presents limited rate performance (45 mAh g−1 at 10C) and higher values in both AC impedance and DC-method derived resistance. A characteristic double “w”-shape curve of DC resistance against cell potential can be possibly considered as an indicator to probe the material structure transition during the charge/discharge process of the cell.
The proton diffusion coefficient for both fresh and heat-treated (140 and 230°C, respectively) α and β-PbO2 electrodes was estimated at room temperature using Galvanostatic Intermittent Titration Technique (GITT). PbO2 samples were prepared by electroformation of cured plates. HSbO3·xH2O with a conductivity of 3.29×10−3 Ω−1 cm−1, was used as solid protonic conductor (SPC) electrolyte. It was found that when structural water is removed, the capacity of both α and β-PbO2 electrodes decreases and the ohmic drop increases. The departure of structural water affects considerably the value of proton diffusion coefficient.
One of the major problems in the development of lithium-ion batteries is the relatively low capacity of cathode materials compared to anode materials. Owing to its high theoretical capacity, vanadium oxide is widely considered as an attractive cathode candidate. However, the main hindrances for its application in batteries are its poor capacity retention and low rate capability. Here, we report the development of multi-shelled vanadium oxide hollow microspheres and their related electrochemical properties. In contrast to the conventional cation-adsorption process, in which the metal cations adsorb on negatively charged carbonaceous templates, our approach enables the adsorption of metal anions. We demonstrate controlled syntheses of several multi-shelled metal oxide hollow microspheres. In particular, the multi-shelled vanadium oxide hollow microspheres deliver a specific capacity of 447.9 and 402.4 mAh g−1 for the first and 100th cycle at 1,000 mA g−1, respectively. The significant performance improvement offers the potential to reduce the wide capacity gap often seen between the cathode and anode materials.
Weight, computing load, sensor load and possibly higher drag may increase the energy use of automated electric vehicles relative to human-driven electric vehicles, although this increase may be offset by smoother driving. Here, we use a vehicle dynamics model to evaluate the trade-off between automation and electric vehicle range and battery longevity. We find that automation will likely reduce electric vehicle range by 5–10% for suburban driving and by 10–15% for city driving. The effect on range is strongly influenced by sensor drag for suburban driving and computing loads for city driving. The impact of automation on battery longevity is negligible. While some commentators have suggested that the power and energy requirements of automation mean that the first automated vehicles will be gas–electric hybrids, our results suggest that this need not be the case if automakers can implement energy-efficient computing and aerodynamic sensor stacks.
Drought is one of the major stresses limiting plant growth and productivity. Drought tolerance is regulated by multiple plant traits and examining the tolerance mechanisms from adapted species would assist in identification of novel pathways and superior genes. Since cellular tolerance is one of the major traits in drought acclimation we made in this study, an attempt to prospect candidate genes associated with the trait in drought hardy crop plant, finger millet (Eleusine coracana (L.) Gaertn). A novel gravimetric approach was employed to simulate field level drought stress for examining stress responsiveness of a few selected genes implicated in different stress response pathways. Gene expression was studied initially by e-northern analysis, and subsequently in leaf tissues experiencing different levels of drought stress by semi-quantitative and quantitative RT-PCR. A few stress responsive genes identified include metallothionein, farnesylated protein ATFP6, protein phosphatase 2A, RISBZ4 and farnesyl pyrophosphate synthase which probably have crucial roles in imparting hardiness to finger millet. Taken together the results suggest that multiple cellular tolerance pathways operate in a coordinated manner in drought tolerant crops.
The cycle behaviour and rate performance of solid-state Li/LiFePO4 polymer electrolyte batteries incorporating the N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR13TFSI) room temperature ionic liquid (IL) into the P(EO)20LiTFSI electrolyte and the cathode have been investigated at 40°C. The ionic conductivity of the P(EO)20LiTFSI+PYR13TFSI polymer electrolyte was about 6×10−4 Scm−1 at 40°C for a PYR13 +/Li+ mole ratio of 1.73. Li/LiFePO4 batteries retained about 86% of their initial discharge capacity (127mAhg−1) after 240 continuous cycles and showed excellent reversible cyclability with a capacity fade lower than 0.06% per cycle over about 500 cycles at various current densities. In addition, the Li/LiFePO4 batteries exhibited some discharge capability at high currents up to 1.52mAcm−2 (2C) at 40°C which is very significant for a lithium metal-polymer electrolyte (solvent-free) battery systems. The addition of the IL to lithium metal-polymer electrolyte batteries has resulted in a very promising improvement in performance at moderate temperatures.
Nanoparticles of lithium cobalt oxide (LiCoO2) were synthesized by means of a citrate sol–gel combustion route. The particles were characterized by scanning and transmission electron microscopies (SEM and TEM), energy-dispersive X-ray spectroscopy, and X-ray diffraction (XRD) measurements. Near spherical nanoparticles of around 100 nm were observed in SEM and TEM micrographs. XRD data indicated that the as-prepared nanoparticles presented pure phase of LiCoO2 with R-3m symmetry. The kinetics of electrochemical intercalation of lithium into the nanoparticles were investigated by means of cyclic voltammetry (CV), chronoamperometry, and electrochemical impedance spectroscopy (EIS) with special emphasis on the application potential as cathode material for aqueous rechargeable lithium batteries. CV studies of the nanoparticles at slow scan rate of 0.1 mV s−1 between 600 and 820 mV versus Ag/AgCl, demonstrated that the nanoparticles represented well-defined reversible peaks. The non-linear chemical diffusion of lithium into the nanoparticles was explored by EIS. In this regards, the results were discussed based on an equivalent circuit, distinguishing the kinetic properties of lithium intercalation. The kinetic parameters of lithium intercalation were obtained using the equivalent circuit, which were in good agreement with the experimental results. The changes of kinetic parameters of lithium intercalation with potential were also discussed in detail.
A High-Temperature Metal–Air Battery (HTMAB) that operates based on a simple redox reaction between molten metal and atmospheric oxygen at 600–1000 °C is presented. This innovative HTMAB concept combines the technology of conventional metal–air batteries with that of solid oxide fuel cells to provide a high energy density system for many applications. Electrochemical reversibility is demonstrated with 95% coulomb efficiency. Cell sealing has been identified as a key issue in order to determine the end-of-charge voltage, enhance coulomb efficiency and ensure long term stability. In this work, molten Sn is selected as anode material. Low utilization of the stored material due to precipitation of the SnO2 on the electrochemically active area limits the expected capacity, which should theoretically approach 903 mAh g−1. Nevertheless, more than 1000 charge/discharge cycles are performed during more than 1000 h at 800 °C, showing highly promising results of stability, reversibility and cyclability.
Two polymer electrolytes (PEs), one consisting of 1M LiPF6 in ethylene carbonate (EC)/dimethyl carbonate (DMC) (PEEC/DMC) and the other consisting of LiTFSI in room temperature ionic liquid (RTIL), 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide (EMITFSI) (PEIL), were prepared by using electrospun P(VdF-HFP) membranes. The PEs showed typical impedance spectroscopic responses with high conductivity and good anodic stability. The PEs were applied with carbon coated LiMn0.4Fe0.6PO4 cathode material prepared by sol–gel method. The charge–discharge kinetics of LiMn0.4Fe0.6PO4 cathode cells were studied by electrochemical impedance spectroscopy. The excellent performance with high capacity and good cycle stability was observed for both the cells. The cell comprising of PEIL showed a better performance than the other cell. The cells having PEEC/DMC and PEIL delivered discharge capacities of 150 and 141mAhg−1, and 168 and 162mAhg−1, respectively, after cycle 1 and 50. The differences in the performance of the PEs originate from the differences in viscosity, ionic conductivity and also from the different levels of interactions of a RTIL and EC/DMC with the polymer. The evaluation of lithium ion diffusion coefficients shows its fast diffusion in both the cases, the trend of which changed with the increase in the number of cycles.
Sol–gel synthesized yttria-stabilized zirconia (YSZ) ceramic powders were coated on LiCoO2 cathode particles by a simple mechano-thermal process, calcined at 923K for 10h. The XRD patterns of YSZ-coated LiCoO2 revealed a single-phase hexagonal α-NaFeO2-type structure with R 3 ¯ m symmetry of the core material without any modification. The surface of LiCoO2 particles was coated with a uniform layer of YSZ that had an average thickness of ∼20nm, as observed from TEM images. The different binding energies of O 1s XPS data exhibited the presence of oxygen ions corresponding to the surface coated YSZ and LiCoO2. The galvanostatic cycling studies for the coated materials suggest that 2.0wt.% YSZ-coated LiCoO2 delivered a stable capacity of 160mAhg−1 between 2.75V and 4.4V vs. Li and a good cycle stability of about 142 cycles. The impedance growth was slower for LiCoO2 surface coated with YSZ, when cells were charged at 4.4V and 4.5V. DSC results illustrated that the oxygen evolution exothermic peak at about 458K was significantly smaller for YSZ-coated cathode materials.
We present a new design of a lithium gel-polymer battery, fabricated with a (LILP) composite consisting of a lithium salt dissolved in an ionic liquid (binary Li-IL) and an ultra high molecular weight ionic liquid polymer (ILP). This polymer, with a Mw of over a million, was prepared by the bulk radical polymerization of a novel ionic liquid monomer, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI). The polymer could form a binary Li-IL solid at a concentration of only 5wt%. We selected high power-active electrode materials, and combined them with the LILP system. The demonstration vapor-free cell had a higher discharge performance than a conventional lithium polymer battery: at 40°C, it retained 83% of its discharge capacity at a 3C current, and relatively good cycle performance. This is the first report of to knowledge that a lithium ion cell with a LILP system performed, in terms of cell performance and cycle durability, at a level of practical utility.
New development and technological innovations make electrical and electronic equipment (EEE) more functional by using an increasing number of metals, particularly the critical metals (e.g. rare and precious metals) with specialized properties. As millions of people in emerging economies adopt a modern lifestyle, the demand for critical metals is soaring. However, the increasing demand causes the crisis of their supply because of their simple deficiency in the Earth’s crust or geopolitical constraints which might create political issues for their supply. This paper focuses on the sustainable supply of typical critical metals (indium, rare earth elements (REEs), lithium, cobalt and precious metals) through recycling waste electrical and electronic equipment (WEEE). To illuminate this issue, the production, consumption, expected future demand, current recycling situation of critical metals, WEEE management and their recycling have been reviewed. We find that the demand of indium, REEs, lithium and cobalt in EEE will continuously increasing, while precious metals are decreasing because of new substitutions with less or even without precious metals. Although the generation of WEEE in 2014 was about 41.9 million tons (Mt), just about 15% (6.5 Mt) was treated environmentally. The inefficient collection of WEEE is the main obstacle to relieving the supply risk of critical metals. Furthermore, due to the widespread use in low concentrations, such as indium, their recycling is not just technological problem, but economic feasibility is. Finally, relevant recommendations are point out to address these issues.
Theoretical ideas of sustainability of heritage are applied to a practical case study. The south western peninsula of England has a rich variety of coastal heritage, analysis of which is undertaken via the ‘fields’ of nature, landscape, buildings, sites, artefacts, activities and people. The value of treating the cultural heritage apart from the natural heritage is seriously questioned, particularly in a coastal context. Disputes relating to the preference for one type of heritage over another are identified. While major successes are demonstrated in landscape and urban conservation, numerous failures and challenges are also recognised. It is argued that, reflecting institutional dominance of the conservation agenda, the heritage most at risk is often that which carries most meaning for local people and traditional visitors. Relating the study to the sustainability dimensions of economic development and environmental protection, the paper questions whether these wider definitions of sustainability can be applied to coastal heritage, especially in a remote region.
New ternary yttrium-based alloys belonging to the R–Y–Ni system (R=La, Ce), with general formula La1−x Ce x Y2Ni9 (0≤x≤1) have been synthesized, and their hydrogen absorption–desorption properties have been investigated through solid gas and electrochemical measurements. The thermodynamic data determined here (hydrogen absorption capacities and hydride formation pressures) are consistent with their application as negative electrode materials in alkaline medium. The electrochemical study shows promising results for La-rich compositions in terms of discharge capacity, rate capability and cycling behavior. The influence of cerium substitution on the negative electrode behavior is discussed.
We introduce a novel formulation concept to prepare high capacity graphite electrodes for lithium ion batteries. The concept is based on the capillary suspension phenomenon: graphite and conductive agent are dispersed in an aqueous binder solution and the organic solvent octanol is added as immiscible, secondary fluid providing the formation of a sample-spanning network resulting in unique stability and coating properties. No additional processing steps compared to conventional slurry preparation are required. The resulting ultra-thick electrodes comprise mass loadings of about 16.5 mg cm−2, uniform layer thickness, and superior edge contours. The adjustment of mechanical energy input ensures uniform distribution of the conductive agent and sufficient electronic conductivity of the final dry composite electrode. The resulting pore structure is due to the stable network provided by the secondary fluid which evaporates residue-free during drying. Constant current-constant potential (CC-CP) cycling clearly indicates that the corresponding microstructure significantly improves the kinetics of reversible Li+ (de-) intercalation. A double layer electrode combining a conventionally prepared layer coated directly onto the Cu current collector with an upper layer stabilized with octanol was prepared applying wet-on-wet coating. CC-CP cycling data confirms that staged porosity within the electrode cross section results in superior electrochemical performance.
In the present work, a new class of high entropy materials for energy storage applications is introduced. Multi-anionic and -cationic compounds are prepared by facile mechanochemistry using a recently designed multi-cationic transition-metal-based high entropy oxide as the precursor and LiF or NaCl as the reactant, leading to formation of lithiated or sodiated materials. Notably, the Li-containing entropy-stabilized oxyfluoride described herein (Lix(Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)OFx) exhibits a working potential of 3.4 V vs. Li+/Li, enabling its use as a cathode active material. Unlike conventional (non-entropy-stabilized) oxyfluorides, this new material shows enhanced Li storage properties due to entropy stabilization, which, in general, facilitates tailoring the cycling performance by varying the constituent elements in yet unprecedented ways. In addition, we demonstrate that the concept of entropy stabilization is also applicable to Na-containing oxychlorides with a rock-salt structure, thus paving the way toward development of (next-generation) post-Li battery technologies.
Unattended wireless sensor networks (UWSNs) are wireless sensor networks characterized by sporadic sink presence and operation in hostile settings. The absence of the sink for period of time prevents sensor nodes to offload data in real time and offers greatly increased opportunities for attacks resulting in erasure, modification, or disclosure of sensor-collected data. In this paper, we focus on UWSNs where sensor nodes collect and store data locally and try to upload all the information once the sink becomes available. One of the most relevant issues pertaining UWSNs is to guarantee a certain level of information survivability in an unreliable network and even in the presence of a powerful attackers. In this paper, we first introduce an epidemic-domain inspired approach to model the information survivability in UWSN. Next, we derive a fully distributed algorithm that supports these models and give the correctness proofs.