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The genotoxic potential of the natural neurotoxin Tetrodotoxin (TTX) was evaluated in a battery of in vitro and in vivo genotoxicity assays. These comprised a bacterial reverse-mutation assay (Ames test), an in vitro human lymphocyte chromosome-aberration assay, an in vivo mouse bone-marrow micronucleus assay and an in vivo rat-liver UDS assay. Maximum test concentrations in in vitro assays were determined by the TTX limit of solubility in the formulation vehicle (0.02% acetic acid solution). In the Ames test, TTX was tested at concentrations of up to 200μg/plate. In the chromosome-aberration assay human lymphocytes were exposed to TTX at concentrations of up to 50μg/ml for 3 and 20h in the absence of S9, and for 3h in the presence of S9. For the in vivo assays, maximum tested dose levels were determined by the acute lethal toxicity of TTX after subcutaneous administration. In the mouse micronucleus assay TTX dose levels of 2, 4 and 8μg/kg were administered to male and female animals, and bone-marrow samples taken 24 and 48h (high-dose animals only) after administration. In the UDS assay, male rats were given TTX on two occasions with a 14-h interval at dose levels of 2.4 and 8μg/kg, the last dose being administered 2h before liver perfusion and hepatocyte culturing. Relevant vehicle and positive control cultures and animals were included in all assays. TTX was clearly shown to lack in vitro or in vivo genotoxic activity in the assays conducted in this study. The results suggest that administration of TTX as a therapeutic analgesic agent would not pose a genotoxic risk to patients.
This study focuses on preparing a hybrid electrolyte, the combination of 90wt% inorganic solid and 10wt% organic liquid, for lithium based rechargeable batteries to illustrate the effect of electrode/electrolyte interfacing on electrochemical performance. The inorganic solid electrolyte selected is Li1.3Ti1.7Al0.3(PO4)3, and the Li-ion conducting organic liquid electrolyte selected is 1M LiPF6 in EC:DEC. Because of the addition of Li-ion conducting liquid between the solid electrode and solid electrolyte, the hybrid electrolyte cell minimizes the ineffective solid-on-solid interfaces common in all-solid-state cells. It is also expected that using a liquid electrolyte at the point of contact between the solid electrolyte and the electrode will adjust for the volume change of the electrode during Li insertion/extraction. As a result, the electrochemical performance of the hybrid electrolyte cell is superior to that of a solid electrolyte cell and is also competitive to that of a pure liquid electrolyte coin cell. Another advantage of the hybrid electrolyte cell observed in this work is that this system behaves as a self-safety device when sudden, higher temperatures are applied.
The effects of the coatings Al2O3, LiAlO x , ZrO2, TiO2, AlPO4, and LiPON and of the electrolyte additives 3-hexylthiophene and lithium difluoro (oxalato)borate (LiDFOB) on the voltage fade phenomenon in 0.5Li2MnO3·0.5LiNi0.375Mn0.375Co0.25O2 cathodes were investigated. Cells containing these materials or additives were cycled according to a standard protocol at room temperature between 2.0 and 4.7 V vs. Li+/Li. As expected, the cells containing either an additive or a coated cathode displayed less capacity loss than cells containing an uncoated cathode and no additive. The voltage fade phenomenon was quantified in terms of changes in the average cell voltage (Wh/Ah). The results indicate that, within experimental error, all of the coatings and additives produced little-to-no effect on voltage fade.
Lithium-mediated nitrogen reduction is a proven method to electrochemically synthesize ammonia; yet the process has so far been unstable, and the continuous deposition of lithium limits its practical applicability. One major problem of further developing this process is that very little is understood about the mechanism. We develop a model to start understanding the kinetics and we use our understanding to develop a potential cycling procedure. We show experimentally that it improves stability of the system, and leads to a significant increase in faradaic efficiency.
With the bloom of portable and wearable electronics, electrochemical storage devices featured with high performance, low-cost, safe, environmental-friendly, lightweight, thin and flexible features become more important than ever. Here, we construct a rechargeable Ni/Zn battery with a Co-doped Ni(OH)2 (CNH) and Zn materials on nickel nanowire arrays (NNA) for electrodes. The CNH cathodic material can be electrochemically deposited onto the NNA, which can deliver a high capacity of 346mAhg−1 at current density of 5Ag−1. Co doping can effectively stabilize Ni(OH)2 with only ~10% capacity loss over 5 000 charge/discharge cycles at 30Ag−1. For anode, the design of Zn on NNA considerably lowers the risk of corrosion and dendrite form ation. As a result, ultrafast rechargeable Ni/Zn batteries are obtained, exhibiting a cell voltage of ~1.75V, energy density of 148.54Whkg−1 (4.05WhL−1) and power density of 1.725kWkg−1 (based on the mass of active materials) with a charging time of <1min. Additionally, the NNA-based aqueous Ni/Zn battery exhibits superior longevity (only ~12% capacity losses after 5000 cycles). These features enable our Ni/Zn batteries a highly promising candidate for the next generation of flexible energy storage systems.
Li–air or Li–oxygen batteries promise significantly higher energies than existing commercial battery technologies, yet their development has been hindered by a lack of suitable electrolytes. In this article, we evaluate the physical properties of varied electrolyte compositions to form generalized criteria for electrolyte design. We show that oxygen transport through non-aqueous electrolytes has a critical impact on the discharge rate and capacity of Li–air batteries. Through experiments and molecular dynamics simulations, we highlight that the choice of salt species and concentration have an outsized influence on oxygen solubility, while solvent choice is the major influence on oxygen diffusivity. The stability of superoxide reaction intermediates, key to the oxygen reduction mechanism, is also affected by variations in salt concentration and the choice of solvent. The importance of reactant transport is confirmed through Li–air cell discharge, which demonstrates good agreement between the observed and calculated mass transport-limited currents. These results showcase the impact of electrolyte composition on transport in metal–air batteries and provide guiding principles and simulation-based tools for future electrolyte design.
Transitions metal sulfides/oxides have been considered as promising anode candidates for next generation lithium-ion batteries (LIBs) due to high theoretical capacities. However, the large volume change during lithiation/delithiation process and poor electronic conductivity often result in a poor charging/discharging performance. Herein, we design a flower-like FeS/Fe2O3 composite via a simple “solvothermal-oxidation” method, in which the Fe2O3 is most distributed on the surface of the flower. The unique porous structure and synergistic effect between FeS and Fe2O3 not only accommodate the large volume expansion, but also facilitate Li ion and electron transport. The Fe2O3 shell effectively reduce the dissolution of Li2Sx during discharge/charge process. When serving as the anode material in lithium ion battery, FeS/Fe2O3 exhibits superior specific capacity, rate capacity and cycling stability compared with pure FeS and Fe2O3.
We studied the influence of temperature on the output performance of triboelectric generators (TEGs). PTFE film and aluminum foil are used as the contact materials for the TEG. A high temperature system and a low temperature system were used to conduct measurements of TEG output voltage and current from 300K to 500K and from 77K to 300K, respectively. Dependence of output performance on temperature was subsequently obtained by statistically analyzing the data as a function of temperature. The performance of the TEG is maximized at around 260K and degrades at both higher and lower temperatures. A possible mechanism is proposed for explaining the observed phenomenon. Applicability of TEG over a wide range of temperature was confirmed, from as low as 77K to as high as 500K, spanning a range of 423K. Several LEDs connected in series were successfully lit up by TEG as the sole power source at temperatures of 77K, 300K and 500K.
The effect of chemical substitution on improving cycle performance of orthorhombic LiMnO2 (o-LiMnO2) was studied at the nominal compositions of LiMn0.95−x M x Cr0.05O2; M=Al, Ga, Yb and In, 0.01<x<0.07. Samples obtaining single phase were synthesized by hydrothermal technique. As the result of studies, LiMn0.92In0.03Cr0.05O2 was confirmed as the optimum composition. The crystal structure refinement showed that chemical substitution varied the average ionic radii of cation sites in o-LiMnO2. The ratio of average ionic radius at Mn site to that of Li site of the optimum compound was 0.87. This value was larger than that of no-substituted LiMnO2; 0.84. TEM observation revealed that stacking faults were observed in the LiMn0.92In0.03Cr0.05O2 grains. It is assumed that these two factors, controlling ionic radii and introducing stacking faults, are key parameters for improving cycle performance. However X-ray diffraction data and discharge curves suggested that phase transformation from orthorhombic to cubic spinel occurred during charge–discharge cycle.
Battery thermal management (BTM) system plays a key part in vehicle thermal safety. A novel method employing water evaporation is presented in this paper. The thin sodium alginate film (SA-1 film) with water content of 99 wt% is prepared using a simple spraying method, and is attached on the surface of battery pack to explore its effectiveness on preventing heat accumulation. The result shows that under the condition with constant current charge/discharge larger than 1 C, the temperature rise rate is reduced by half. Under the condition with the New Europe Drive Cycle, the temperature could maintain stable without obvious rise. Moreover, a simple water automatic-refilling system is designed to address the dry issue of the film in terms of evaporation elimination. The proposed SA-1 film BTM system shows to be a very convenient and efficient approach in handling the thermal surge of Li-ion batteries without any change in battery pack integration and assembly.
Metal oxide (Co3O4) was coated on spinel Li1.1Mn1.9O4 using glutamic acid. Powder X-ray diffraction pattern of Co3O4-coated spinel Li1.1Mn1.9O4 showed that the Co3O4 coating medium was not incorporated in the spinel bulk structure. Morphology of the Co3O4-coated spinel Li1.1Mn1.9O4 was observed by scanning electron microscopy and transmission electron microscopy. The cycling performance of the Co3O4-coated spinel Li1.1Mn1.9O4 was obviously improved, compared to the pristine Li1.1Mn1.9O4 at elevated temperature (55°C). Improvement of rate capability was also achieved at high C-rates.
In this work, we propose a novel electrolyte additive phenyl trifluoromethyl sulfide (PTS) to improve the interfacial stability of high voltage lithium nickel manganese oxide (LiMn1.5Ni0.5O4) cathode/electrolyte. At 1C rate, addition of 0.5% PTS improves the capacity retention of LiNi0.5Mn1.5O4 from 65% to 84% after 450 cycles at room temperature, and from 64% to 95% after 100 cycles at evaluate temperature. Density functional theory calculation and experimental characterization demonstrate that PTS oxidizes preferentially to the carbonate base electrolyte, generating a SEI film, which effectively suppresses the continuous decomposition of carbonate base electrolyte and the structural destruction of LiMn1.5Ni0.5O4.
The cross-linked composite polymer electrolytes composed of poly(ethylene oxide) (PEO), hyperbranched polymer with terminal acryloyl groups (poly-1b), poly(ethylene glycol) methyl ether methacrylate (PEOMA), LiN(CF3SO2)2 were prepared, and their ionic conductivities, mechanical strength, electrochemical and thermal properties, and interfacial stabilities with electrodes were investigated. The ionic conductivity increased with an increase in the PEOMA content in the cross-linked composite polymer electrolyte, and the highest ionic conductivity was obtained at the [80% PEO/20% (poly-1b/PEOMA)]12(LiN(CF3SO2)2) electrolyte with the poly-1b/PEOMA ratio of 1/3. However, the tensile strength decreased with an increase in the PEOMA content in the cross-linked composite polymer electrolytes. The cross-linked composite polymer electrolyte with the highest ionic conductivity has three times higher tensile strength than non-cross-linked (80% PEO/20% poly-1a)12(LiN(CF3SO2)2) electrolyte. The addition of the PEOMA unit into the cross-linked composite polymer electrolyte improved both the ionic conductivity and mechanical property at the same time. And also, the cross-linked composite polymer electrolyte containing the PEOMA unit showed the good interfacial stability with both lithium metal and cathode electrodes.
Shape memory polymers (SMPs) are a class of smart materials which can recover their shape even after many shape changes in application of an external stimulus. In this paper, flexural behavior of a composite beam, constructed of a corrugated part filled with SMPs, is studied. This composite beam is applicable in sensor and actuator applications. Since the corrugated profiles display higher stiffness-to-mass ratio in the transverse to the corrugation direction, the beams with a corrugated part along the transverse direction are stiffer than ones with a corrugated part along the length. Employing a developed constitutive model for SMPs and the Euler–Bernoulli beam theory, the behavior of the composite beam is studied. Since the utilized constitutive model is in the integral form, the finite-difference-method is used for discretizing the equations. It is shown that load capacity is increased in both composite beams compared to a pure SMP beam. This bigger load capacity is obtained by a low decrease in shape fixity. In addition, for different corrugated shapes (trapezoidal, pseudo-sinusoidal and triangular) with the same SMP content, the beam response is obtained. Finally, the results of the constrained stress-recovery are obtained and the effects of mechanical properties on its behavior, are studied.
Lithium-ion batteries (LIBs) are considered as a promising power source for electric vehicles and electronic products such as mobile phones, laptops, and tablets. The anode material plays a crucial role in the reliability and safety of LIBs. Among the anode candidates, MLi2Ti6O14 (M = 2Na, Sr, Ba, Pb) materials have very good prospects due to their excellent safety, good structure stability, negligible volume change, and suitable voltage plateau of about 1.3–1.4 V (vs. Li0/Li+). However, MLi2Ti6O14 materials frequently sustain serious capacity decay at high rate due to the poor electronic and ionic conductivities. Therefore, it is very meaningful to summarize comprehensively and scientifically the advances of this material family from all aspects. The main objective of the review is aimed to summarize various proposed strategies (i.e. material treatment, morphology control, surface modification, and cation doping) and the breakthroughs to enhance the rate capacity and cycling stability of the MLi2Ti6O14 materials. The review will provide some insights into the structures and performance issues, which will be helpful for the design and optimization of the MLi2Ti6O14 materials.
The network described in this paper has been set up to provide detailed time-series data on concentrations of 222Rn in air at various locations within the Alligator Rivers Region, over a time frame of several years. These data will be important in assessing the effects of uranium mining operations on radon levels in the region, both in providing baseline and monitoring data and in calibrating and verifying predictive models. At present, three stations are operating in the region with a fourth being commissioned. Each station logs half hourly average radon concentrations and relevant meteorological data (wind speed, direction and variability, air pressure and temperature, relative humidity, soil temperature, rain and sunshine rates). It is intended to operate the four stations at selected locations for one- or two-year intervals, at the end of which three will be moved to new locations (one station at Mudginberri will be kept as a constant control station). Sites for which extensive datasets are currently available include: Jabiru Town, Jabiru East, Djarr Djarr, East Alligator Ranger Station and Nabarlek minesite. Illustrative data from these sites are presented.
A fundamental electrochemical model is developed, describing the capacity fade of C6/LiFePO4 batteries as a function of calendar time and cycling conditions. At moderate temperatures the capacity losses are mainly attributed to Li immobilization in Solid-Electrolyte-Interface (SEI) layers at the anode surface. The SEI formation model presumes the availability of an outer and inner SEI layers. Electron tunneling through the inner SEI layer is regarded as the rate-determining step. The model also includes high temperature degradation. At elevated temperatures, iron dissolution from the positive electrode and the subsequent metal sedimentation on the negative electrode influence the capacity loss. The SEI formation on the metal-covered graphite surface is faster than the conventional SEI formation. The model predicts that capacity fade during storage is lower than during cycling due to the generation of SEI cracks induced by the volumetric changes during (dis)charging. The model has been validated by cycling and calendar aging experiments and shows that the capacity loss during storage depends on the storage time, the State-of-Charge (SoC), and temperature. The capacity losses during cycling depend on the cycling current, cycling time, temperature and cycle number. All these dependencies can be explained by the single model presented in this paper.
is Product Manager Advanced High-strength Steels at Thyssenkrupp Steel Europe AG in Duisburg (Germany).
Cycling efficiency and rate capability of porous copper-coated, amorphous silicon thin-film negative electrodes are compared to equivalent silicon thin-film electrodes in lithium-ion batteries. The presence of a copper layer coated on the active material plays a beneficial role in increasing the cycling efficiency and the rate capability of silicon thin-film electrodes. Between 3C and C/8 discharge rates, the available cell energy decreased by 8% and 18% for 40nm copper-coated silicon and equivalent silicon thin-film electrodes, respectively. Copper-coated silicon thin-film electrodes also show higher cycling efficiency, resulting in lower capacity fade, than equivalent silicon thin-film electrodes. We believe that copper appears to act as a glue that binds the electrode together and prevents the electronic isolation of silicon particles, thereby decreasing capacity loss. Rate capability decreases significantly at higher copper coating thicknesses as the silicon active material is not accessed, suggesting that the thickness and porosity of the copper coating need to be optimized for enhanced capacity retention and rate capability in this system.
Multi-shell structured binary transition metal oxide powders with a Ni/Co mole ratio of 1:2 are prepared by a simple spray drying process. Precursor powder particles prepared by spray drying from a spray solution of citric acid and ethylene glycol have completely spherical shape, fine size, and a narrow size distribution. The precursor powders turn into multi-shell powders after a post heat-treatment at temperatures between 250 and 800 °C. The multi-shell structured powders are formed by repeated combustion and contraction processes. The multi-shell powders have mixed crystal structures of Ni1−x Co2O4−x and NiO phases regardless of the post-treatment temperature. The reversible capacities of the powders post-treated at 250, 400, 600, and 800 °C after 100 cycles are 584, 913, 808, and 481 mA hg−1, respectively. The low charge transfer resistance and high lithium ion diffusion rate of the multi-shell powders post-treated at 400 °C with optimum grain size result in superior electrochemical properties even at high current densities.
Mesoporous LiFePO4/C microsphere was successfully prepared by spray drying assisted template method (SDATM) with citric acid as a template. This material has an average pore size of 50nm and gives large specific surface area (32.2m2 g−1) with evenly distributed carbon (4.3wt.%). It is also easy to bring into contact with electrolyte, facilitate the electric and lithium ion diffusion. It presents large reversible capacity of 158.8mAhg−1 at C/10, even high rate capacity of 59.7mAhg−1 at 20C, and excellent capacity retention rate closed to 95.5% after various current densities.
Pseudocapacitive materials are highly capable to achieve high energy density integrated with high power electrostatic capacitive materials. However, finding a suitable electrostatic capacitive material to integrate with pseudocapacitive material in order to achieve high energy density with good rate capability is still a challenge. Herein, we are providing a novel synthetic approach starting from the synthesis of polypyrrole nanotubes (PPy-NTs) and ending up at the carbonization of PPy-NTs to obtain N-doped carbon nanotubes (N-CNTs). With highly porous nature of PPy-NTs and great graphitic texture with copious heteroatom functionalities, N-CNTs significantly promoted the faradic pseudo-capacitors, demonstrating high single-electrode capacitance over 332 F/g(PPy-NTs) and 228 F/g(N-CNTs) in 1 M H2SO4 aqueous solution. Further, a novel asymmetric supercapacitor with PPy-NTs as positive and N-CNTs as negative electrode has been fabricated. This PPy-NTs//N-CNTs cell effectively provides high operation voltage (1.4 V) and hence high energy density over 28.95 W h/kg (0.41 mW h/cm3) with a high power density of 7.75 kW/kg (113 mW/cm3) and cyclic stability of 89.98% after 2000 cycles.
Electrochemical behavior of the composite electrodes containing Li2.6Co0.4N and nano-size SiO1.1 has been investigated with the solid poly (ethylene oxide) electrolytes at various temperatures. The composite electrodes have a high first cycle efficiency of ca. 100% and a large reversible capacity of ca. 500mAhg−1. Result reveals that the operating temperature and the electrode composition dominate the cycling performance. Dispersing a certain amount of sub-micro ceramic BaTiO3 within the electrodes is favorable for improving the morphology stability of the composite electrodes at the elevated temperature. Some factors influencing the electrode properties are presented and discussed in detail.
In this paper, a bio-hydrometallurgical route based on fungal activity of Aspergillus niger was evaluated for the detoxification and recovery of Cu, Li, Mn, Al, Co and Ni metals from spent lithium-ion phone mobile batteries under various conditions (one-step, two-step and spent medium bioleaching). The maximum recovery efficiency of 100% for Cu, 95% for Li, 70% for Mn, 65% for Al, 45% for Co, and 38% for Ni was obtained at a pulp density of 1% in spent medium bioleaching. The HPLC results indicated that citric acid in comparison with other detected organic acids (gluconic, oxalic and malic acid) had an important role in the effectiveness of bioleaching using A. niger. The results of FTIR, XRD and FE-SEM analysis of battery powder before and after bioleaching process confirmed that the fungal activities were quite effective. In addition, bioleaching achieved higher removal efficiency for heavy metals than the chemical leaching. This research demonstrated the great potential of bio-hydrometallurgical route to recover heavy metals from spent lithium-ion mobile phone batteries.