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Photosystem II (PSII) is a multi-subunit enzyme responsible for solar-driven water oxidation to release O2 and highly reducing electrons during photosynthesis. The study of PSII in protein film photoelectrochemistry sheds light into its biological function and provides a blueprint for artificial water-splitting systems. However, the integration of macromolecules, such as PSII, into hybrid bio-electrodes is often plagued by poor electrical wiring between the protein guest and the material host. Here, we report a new benchmark PSII–electrode system that combines the efficient wiring afforded by redox-active polymers with the high loading provided by hierarchically-structured inverse opal indium tin oxide (IO-ITO) electrodes. Compared to flat electrodes, the hierarchical IO-ITO electrodes enabled up to an approximately 50-fold increase in the immobilisation of an Os complex-modified and a phenothiazine-modified polymer. When the Os complex-modified polymer is co-adsorbed with PSII on the hierarchical electrodes, photocurrent densities of up to ∼410 μA cm−2 at 0.5 V vs. SHE were observed in the absence of diffusional mediators, demonstrating a substantially improved wiring of PSII to the IO-ITO electrode with the redox polymer. The high photocurrent density allowed for the quantification of O2 evolution, and a Faradaic efficiency of 85 ± 9% was measured. As such, we have demonstrated a high performing and fully integrated host–guest system with excellent electronic wiring and loading capacity. This assembly strategy may form the basis of all-integrated electrode designs for a wide range of biological and synthetic catalysts.
The Ag4Sn and Ag3Sn intermetallics are successfully synthesized by combining electrochemical deposition and dealloying methods. The Ag4Sn and Ag3Sn possess a half-wave potential of 0.810 mV and 0.790 mV respectively for the oxygen reduction reaction in alkaline media, which are comparable to the commercial Pt/C (0.837 mV). In term of the durability, the Ag4Sn retains a half-wave potential of 0.775 mV after 5000 potential cycles, which is superior to Pt/C of 0.784 mV. The better catalytic activity and durability are mainly attributed to the ensemble effect and strong chemical bond in the AgSn ordered intermetallic structure. The catalytic activity is hardly influenced by methanol or ethanol in alkaline media with alcohol concentrations up to 1.0 M. Therefore, a membraneless alkaline zinc-air battery and direct alcohol fuel cell can operate with Ag4Sn and Ag3Sn intermetallics as the cathode catalysts, which allow the anode fuel to freely enter the cathode. A high power density is delivered by the membraneless alkaline fuel cells with zinc, methanol or ethanol as anode fuels. The excellent alcohol-tolerance is beneficial to the oxygen reduction reaction of alkaline fuel cells and makes the AgSn intermetallics a promising candidate to replace Pt-based electrocatalysts for oxygen reduction reaction.
In the development of supercapacitors and rechargeable batteries based on conducting polymers, the stability of the material is an important concern. The objective of this work is to investigate the electrochemical aging of layer-by-layer (LBL) films of two polymers, namely poly(o-methoxyaniline) and poly(3-thiophene acetic acid), which present a self-doping effect, and compare them with poly(o-methoxyaniline) casting film electrochemical properties. Cyclic voltammetry and impedance spectroscopy are used to analyze the behavior of the films. The results show that POMA/PTAA LBL films have a higher electrochemical stability than POMA casting films. This last one presents a continuous degradation as the number of ageing cycles are increased resulting in an 80% decrease from the initial specific capacitance value after 3000 cycles. For LBL films, on the other hand, film stability has a different behavior, and after 3000 cycles, only 1% of decrease in the specific capacitance is observed. Impedance data shows a continuous increase in both polymer resistance and ionic charge transfer resistance in the case of the POMA casting film whereas no changes is observed for the LBL one indicating the film degradation is possible related to the counter ion intercalation/deintercalation which occurs mainly in POMA samples.
Highly conducting single wall carbon nanotube (SWCNT) networks are functionalized in different ways to achieve multifunctional electrodes. Such electrode material is used as extreme light and thin gas diffusion electrodes in fuel cells. In contrast to previous work, no other carbon material is part of the electrode. We demonstrate that the performance of such SWCNT gas diffusion electrodes is comparable to regular electrodes, which are based on amorphous carbon (a-C). This allows the entire replacement of these regular carbon electrodes by such multifunctionalized SWCNT networks. This way, extremely thin and light gas diffusion electrodes are realized, potentially fulfilling the demands of light weight power supplies.
With the exponential growth of technology in mobile devices and the rapid expansion of electric vehicles into the market, it appears that the energy density of the state-of-the-art Li-ion batteries (LIBs) cannot satisfy the practical requirements. Sulfur has been one of the best cathode material choices due to its high charge storage (1675 mAh g−1), natural abundance and easy accessibility. In this paper, calculations are performed for different cell design parameters such as the active material loading, the amount/thickness of electrolyte, the sulfur utilization, etc. to predict the energy density of Li-S cells based on liquid, polymeric and ceramic electrolytes. It demonstrates that Li-S battery is most likely to be competitive in gravimetric energy density, but not volumetric energy density, with current technology, when comparing with LIBs. Furthermore, the cells with polymer and thin ceramic electrolytes show promising potential in terms of high gravimetric energy density, especially the cells with the polymer electrolyte. This estimation study of Li-S energy density can be used as a good guidance for controlling the key design parameters in order to get desirable energy density at cell-level.
The irreversible mechanisms of lithium insertion in amorphous tin composite oxides SnB0.6P0.4O2.9 have been studied by X-ray diffraction (XRD) and 119 Sn Mössbauer spectroscopy. The determination of the Lamb–Mössbauer factor has allowed us to evaluate the relative numbers of different tin atoms (SnII, Sn0). We show that insertion of lithium reduces the SnII into Sn0 atoms, which form nanoparticles of active species. The lithium ions act as glass modifiers, breaking the bonds within MOM′ (M, M′=B, P, Sn) bridges and forming non-bridging MO δ− bonds.
The steady supply of quality power from the distribution system is a major concern for the sensitive loads. The dynamic voltage restorer system is mainly used to compensate voltage sags and swells for uninterrupted reliable &quality power supply. Hence, this work proposes a novel combination of dynamic voltage restorer and compressed air energy storage for power quality enhancement. The main aim of this work is to replace the conventional battery powered dynamic voltage restorers with the compressed air energy storage powered dynamic voltage restorers. This article presents the design and modeling of a third generation compressed air energy storage system with zero greenhouse gas emission and high response time. Further, a compressed air energy storage powered dynamic voltage restorer (CAESPDVR) connected distribution system supplying a sensitive load is modeled and the voltage variations during various faults are analyzed. The behavior of the system with and without the compressed air energy storage powered dynamic voltage restorer is investigated. MATLAB/Simulink and SimulationX software are used for modeling and analysis.
Hybrid supercapacitors with their improved performance in energy density without altering their power density have been in trend since recent years. The hybrid supercapacitor delivers higher specific capacitance in comparison to the existing electric double layer capacitor (EDLC) and pseudocapacitors. Generally, the asymmetric behavior of hybrid supercapacitors which is the combination of EDLC and pseudocapacitor acts as an enhancer in its respective capacitance values. This asymmetric approach marks a new beginning towards the much-needed pollution free, long lasting and proficient energy-storing performance. Corresponding to their utilization in hybrid electric vehicles and similar sort of power necessity based devices; the research in developing new advanced storage devices finds an enormous and vast future ahead. The most significant factor for the energy efficient applications demands a considerably higher ratio of surface to the volume by incorporation of new materials. This review article gives an overview of recent advances in the development of hybrid supercapacitors, storage mechanism, criteria of formation, components, different electrode and electrolyte materials, electrochemical profile assessment, design fabrication and their applications.
Mesoporous nanoring-like Zn-Co mixed oxides are synthesized via a simple template-free solvothermal method with a subsequent annealing process. The ring-like nanostructures with hollow interiors are formed under the complexing effects of potassium sodium tartrate. Numerous mesopores are generated after the precursor is annealed at 500 °C. When applied as anode materials, the mesoporous nanoring-like Zn-Co mixed oxides can deliver a high discharge capacity of 1102 mAh g−1 after 200 cycles at 500 mA g−1. Even when the current density is increased to 2 A g−1, the mixed oxides can still retain a reversible capacity of 761 mAh g−1. Such high cycling stability and rate capability are mainly derived from the unique mesoporous ring-like nanostructures and the synergistic effects between Zn and Co based oxides.
1,4-Dialkoxybenzene additives are commonly used as redox active shuttles in lithium-ion batteries in order to prevent runaway oxidation of electrolyte when overcharge conditions set in. During this action the shuttle molecule goes through a futile cycle, becoming oxidized at the cathode and reduced at the anode. Minimizing parasitic reactions in all states of charge is paramount for sustained protective action. Here we demonstrate that recently developed bis-annulated 9,10-bis(2-methoxyethoxy)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethano-anthracene shuttle molecule (that yields exceptionally stable radical cations) survives over 120 cycles of overcharge abuse with 100% overcharge ratio at C/5 rate. Equally remarkably, in the presence of this additive the cell impedance becomes significantly lower compared to the control cells without the additive; this decrease is observed during the formation, normal cycling, and even under overcharge conditions. This unusual dual action has not been observed in other redox shuttle systems, and it presents considerable practical interest.
The use of a low temperature geothermal spring together with the heat energy still contained in waste water from the different therapy systems installed in a spa (shower, jets, bathrooms, jacuzzis, pools, ventilation processes) can significantly reduce the operating and maintenance costs of the installation. This covers part of the air conditioning needs of the building and of the heating of thermal water to the appropriate temperature for therapeutic use. In the first part of the study, an analysis of the spring's situation was made, calculating the thermal water needs and presenting the consumption according to the operation schedule on different types of day. In this way, the contribution the spring was capable of giving was compared and the evolution of the thermal water in the tanks was studied. In the second part, the climatic conditions that the spa should meet are studied, along with the loads that it should support, the energy reclaimed from the different heat focuses and the repercussions on the final solution.
The electrochemical behavior of lead, lead–calcium–tin–aluminum and lead–calcium–tin–aluminium–bismuth alloy electrode has been studied in the electrolyte of sulfuric, phosphoric and mixed acid electrolyte. The electrochemical measurements were performed using a cyclic voltammetry technique (CV) with three-electrode system. The results demonstrated that bismuth(III) doped in the lead electrode can increase electrical capacity. The oxidation peak potential of lead alloy electrode in phosphoric acid shifted to the positive compared to that in sulfuric acid. The formation of PbHPO4 in phosphoric acid and its passivation are responsible for the positive shift of the oxidation.
N-doped microporous carbon as an exceptional metal-free catalyst from waste biomass (banana peel as representative) was obtained via fast catalysis carbonization, followed by N-doping modification. The method achieves a relatively high C conversion efficiency of ∼41.9%. The final carbon materials are doped by N (∼3 at.%) and possess high surface area (∼1097 m2 g−1) and abundant micropores. Compared to commercial Pt/C materials, the as-prepared carbon catalyst exhibits a comparable electrocatalytic activity and much better stability. Furthermore, the metal-free catalyst loaded Zn-air battery possesses higher discharge voltage and power density as compared with that of commercial Pt/C. This novel technique can also be readily applied to produce metal-free carbon catalysts from other typical waste biomass (e.g., orange peel, leaves) as the carbon sources. The method can be developed as a potentially general and effective industrial route to transform waste biomass into high value-added microporous carbon with superior functionalities.
Measurements of particles <10μm (PM10) and particle-bound polycyclic aromatic hydrocarbons (pPAH) were performed in different passenger train coaches between Zürich and Berne, the most busy intercity connection in Switzerland. All trains are electrified and the indoor air quality is regulated by a mechanical ventilation system. In the smoker sections, pPAH levels were on average about 250ngm−3, PM10 levels about 950μgm−3. In the non-smoker section, pPAH levels were about 45ngm−3 and PM10 levels about 210μgm−3. Our observations suggest that smoking is the most important source of pPAH and PM10. The spatial variation within the coaches indicates that pPAHs spread out from the smoker compartments into the non-smoker compartments. For PM10, resuspended material may also be a source of airborne PM10 but the contribution within this non-stop connection with most of the passengers being seated all the time was probably small. The influence of outdoor PM10 and pPAH on indoor levels was negligible. Both pollutants, pPAH and PM10 were largely elevated in the smoker as well as in the non-smoker compartments. Despite this fact, a questionnaire on the quality of travelling showed that most of the passengers felt well and only a small proportion felt uneasy.
Self-control and self-management skills (SCMSk) represent a cognitive-behavioral coping skills model that has been successfully applied to assessment and treatment. Nevertheless, no general adult self-report instrument has been developed to measure this important construct. The 16-item Self-Control and Self-Management Scale (SCMS) was developed as a new adult self-report instrument designed to be a general trait measure of SCMSk. In Study 1, the item pool was generated and revised based on the current literature and feedback from content validity experts. In Study 2, based on responses from a multiethnic student sample (n = 302), factor analytic procedures and rational item selection were used to produce a reliable and construct valid instrument. The findings of both studies support the further evaluation of the SCMS as a research and applied instrument, and suggest its potential current use in student and counseling settings given obtained relationships with anxiety, depression, and weight-management competencies.
In this study, a novel mesoporous carbon-encapsulated NiO nanocomposite is proposed and demonstrated for Li-ion battery negative electrode. The nanostructure of the electrode composes of an ordered mesoporous CMK-3 as a 3D nanostructured current collector with micorporous channels for Li+ transportation. In addition, exclusive formation of NiO nanoparticles in the confined space of the ordered mesoporous carbon is achieved using the hydrophobic encapsulation route. The half-cell assembled with the synthesized NiO/CMK-3 nanocomposite is able to deliver a high charge capacity of 812mAhg−1 at the first cycle at a C-rate of 1000mAg−1 and retained throughout the test with only 0.236% decay per cycle. Even the C-rate as high as 3200mAg−1, a charge capacity of 808mAhg−1 contributed by the NiO nanoparticles in CMK-Ni is obtained, which shows excellent rate capability for NiO with utilization close to 100%. The result suggests fast kinetics of conversion reaction for NiO with Li+. It also indicates the blockage of the pore channels by NiO nanoparticles does not take place in the synthesized NiO/CMK-3.
Metal–organic frameworks (MOFs) are attractive electrodes for supercapacitors but generally suffer from low electric conductivity and chemical stability. Here the authors report stable conductive MOFs based on hexaminobenzene linker with volumetric and areal capacitances in excess of 700 F per cm3 and 15 F per cm2, respectively.
It is envisioned that other than the grid-building communication, the smart buildings could potentially treat connected neighborhood buildings as a local buffer thus forming a local area energy network through the smart grid. As the hardware technology is in place, what is needed is an intelligent algorithm that coordinates a cluster of buildings to obtain Pareto decisions on short time scale operations. Research has proposed a memetic algorithm (MA) based framework for building cluster operation decisions and it demonstrated the framework is capable of deriving the Pareto solutions on an 8-h operation horizon and reducing overall energy costs. While successful, the memetic algorithm is computational expensive which limits its application to building operation decisions on an hourly time scale. To address this challenge, we propose a particle swarm framework, termed augmented multi-objective particle swarm optimization (AMOPSO). The performance of the proposed AMOPSO in terms of solution quality and convergence speed is improved via the fusion of multiple search methods. Extensive experiments are conducted to compare the proposed AMOPSO with nine multi-objective PSO algorithms (MOPSOs) and multi-objective evolutionary algorithms (MOEAs) collected from the literature. Results demonstrate that AMOPSO outperforms the nine state-of-the-art MOPSOs and MOEAs in terms of epsilon, spread, and hypervolume indicator. A building cluster case is then studied to show that the AMOPSO based decision framework is able to make hourly based operation decisions which could significantly improve energy efficiency and achieve more energy cost savings for the smart buildings.
Ultracapacitors (UCs) have been widely recognized as an enabling energy storage technology in various industrial applications. They hold several advantages including high power density and exceptionally long lifespan over the well-adopted battery technology. Accurate modeling and State-of-Charge (SOC) estimation of UCs are essential for reliability, resilience, and safety in UC-powered system operations. In this paper, a novel fractional-order model composed of a series resistor, a constant-phase-element (CPE), and a Walburg-like element, is proposed to emulate the UC dynamics. The Grünald-Letnikov derivative (GLD) is then employed to discretize the continuous-time fractional-order model. The model parameters are optimally extracted using genetic algorithm (GA), based on the time-domain data acquired through the Federal Urban Driving Schedule (FUDS) test. By means of this fractional-order model, a fractional Kalman filter is synthesized to recursively estimate the UC SOC. Validation results prove that the proposed fractional-order modeling and state estimation scheme is accurate and outperforms current practice based on integer-order techniques.
Graphite is an important active material for lithium ion battery anode. In the present paper, a kind of graphitized MCMB (MCMB-6-28) was oxidized at 600 or 700°C, and the effects of the oxidation were investigated by cyclic voltammetry (CV) method, electrochemical impedance spectroscopy (EIS), and rectangular potential technique. It was found that the specific surface area of the electrode made of the graphite can be increased notably by the oxidative treatment. Meanwhile, after oxidation, the electrochemical impedance of the graphite electrode is reduced, and the reaction reversibility is improved.
The objective of this work was to test the compliance of commercially available batteries with the German Battery Ordinance, a project of the German government that was initiated by the Federal Environment Agency. Different types of commercially available dry cells were analysed for their cadmium, lead and mercury contents. The dry cells underwent mechanical pre-treatment, separation of the different components and microwave-assisted digestion before determination of the heavy metals. Mercury is sometimes added to prevent the generation of gaseous hydrogen from the electrochemical process. Lead could be present since it is sometimes used as an alloying element of zinc. Cadmium has no technical importance and is an undesirable impurity. None of the batteries contained higher heavy metal mass fractions than the permissible limits.
Electrocatalytic effects associated with the reduction of thionyl chloride in a LiAlCl4–SOCl2 electrolyte solution containing Schiff base metal(II) (metal (M): Co, Ni, Cu and Mn) complexes are evaluated by determining the kinetic parameters for the reactions using cyclic voltammetry at a glassy carbon electrode. The charge-transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. Catalytic effects are demonstrated from both a shift in the reduction potential for the thionyl chloride in a more positive direction and an increase in peak currents. The reduction of thionyl chloride is diffusion controlled. Catalytic effects are larger for thionyl chloride solutions containing M(II)(1,5-bis(salicylidene imino) pentane) (M(II)(SALPE)) rather than M(II)(1,3-bis(salicylidene imino) propane) (M(II)(SALPR)). Significant improvements in cell performance are found in terms of the both thermodynamics and kinetic parameters for the thionyl chloride reduction. An exchange rate constant, k 0, of 1.89×10−8 cms−1 is found at the bare electrode, while larger values of 2.79×10−8 to 2.09×10−6 cms−1 are observed in the case of the catalyst-supported glassy carbon electrode.
Rosin, which is an extract of pine trees, is used as an eco-friendly binder additive to a conventional solvent-based binder, polyvinylidene fluoride (PVdF). The composite binder system is used to evaluate the performance of the Li4Ti5O12 (LTO) electrodes using a range of physical and electrochemical characterization techniques. The addition of rosin decreases the crystallinity of PVdF, disperses the conducting agent and binder well, and ultimately leads to an increase in the diffusivity and cyclic capacity of lithium ions. When the amount of rosin additive to the PVdF binder is 40 wt%, the LTO electrode exhibits the highest cyclic capacity and diffusivity; of 164 mAh g−1 at the 110th cycle and 4.28 × 10−10 cm2 s−1, respectively.