Deep eutectic solvent-based supramolecular gel polymer electrolytes for high-performance electrochemical double layer capacitors

Gel polymer electrolytes (GPEs) can avoid the electrolyte leakage risk of electrochemical double layer capacitors (EDLCs). But aqueous GPEs often suffer from narrow electrochemical windows. Herein, a series of deep eutectic solvent (DES)-based supramolecular GPEs are firstly developed for carbon-based EDLCs with wide voltage windows. The as-fabricated DES-based GPE shows an ionic conductivity of ~58 mS cm^?1, which makes the stable voltage window of a carbon-based EDLC reach 2.4 V. The carbon-based EDLC exhibits a specific capacitance of 32.1 F g^?1, an energy density of 24.6 Wh kg^?1 and a capacitance retention of ~90% after 15,000 charge-discharge cycles. Moreover, when quinhydrone is added into the DES-based GPE, the specific capacitance and energy density of the corresponding EDLC can be further expanded to 60 F g^?1 and 43.6 Wh kg^?1, respectively. Therefore, our work may present a universal strategy to prepare novel supramolecular GPEs for high-performance EDLCs with wide voltage windows.     

Thermodynamic modeling of gas solubility in aqueous sodium chloride solution

An electrolyte Equation of State is presented by combining the Cubic Plus Association Equation of State,Mean Spherical Approximation and the Born equation.This new model uses experimental relative static permittivity,intend to predict well the activity coefficients of individual ions (ACI) and liquid densities of aqueous solutions.This new model is applied to model water + NaCl binary system and water + gas +NaCl ternary systems.The cation/anion-water interaction parameters of are obtained by fitting the exper-imental data of ACI,mean ionic activity coefficients (MIAC) and liquid densities of water + NaCl binary system.The cation/anion-gas interaction parameters are obtained by fitting the experimental data of gas solubilities in aqueous NaCl solutions.The modeling results show that this new model can correlate well with the phase equilibrium and volumetric properties.Without gas,predictions for ACI,MIAC,and liquid densities present relative average deviations of 1.3％,3.6％ and 1.4％ compared to experimental ref-erence values.For most gas-containing systems,predictions for gas solubilities present relative average deviations lower than 7.0％.Further,the contributions of ACI,and salting effects of NaCl on gases are ana-lyzed and discussed.     

Influence of anode current density on carbon parasitic reactions during electrolysis

In the electro-deoxidation process, carbon parasitic reaction (CO₃^2- + 4e^-=C + 3O^2-) usually occurs when using carbon materials as the anode, which leads to increase of the carbon content in the final metal and decrease of the current efficiency of the process. The aim of this work is to reduce the negative effect of carbon parasitic reaction on the electrolysis process by adjusting anode current density. The results indicate that lower graphite anode area can achieve higher current density, which is helpful to increase the nucleation site of CO₂ bubbles. Most of CO₂ would be released from the anode instead of dissolution in the molten CaCl₂ and reacting with O^2- to form CO₃^2-, thus decreasing the carbon parasitic reaction of the process. Furthermore, the results of the compared experiments show that when the anode area decreases from 172.78 to 4.99 cm², CO₂ concentration in the released gases increases significantly, the carbon mass content in the final metal product decreased from 1.09% to 0.13%, and the current efficiency increased from 6.65% to 36.50%. This study determined a suitable anode current density range for reducing carbon parasitic reaction and provides a valuable reference for the selection of the anode in the electrolysis process.     

Contribution of metal vapor mass at periphery part of pulsed arc to electromagnetic force in weld pool

The arc welding has been used in various welding methods because it is inexpensive and high in strength after welding. However, it is a problem that accidents such as collapse of the bridge occur because of the welding defects. The welding of low cost and high productivity is required without the welding defects. The pulsed TIG welding is inexpensive and capable of high‐quality welding. The electromagnetic force contributing to penetration changes because the transient response of arc temperature and iron vapor generated from anode occurs. However, the analysis of pulsed TIG welding with metal vapor has been elucidated only metal vapor concentration near anode with transient phenomenon and heat flux. Thus, the theoretical elucidation of penetration depth with control factor has not been researched. In this paper, the contribution of metal vapor mass at the periphery part of pulsed arc to the electromagnetic force in the weld pool is elucidated. As a result, the iron vapor mass at periphery part decreased with increasing the frequency. The iron vapor was stagnated at axial center within one cycle. The electromagnetic force to the penetration depth direction in weld pool increased at axial center. Therefore, the metal vapor mass at periphery part plays an important role for the electromagnetic force increment at axial center.     

Effect of S on H-induced grain-boundary embrittlement in γ-Fe by first-principles calculations

The effect of interstitial impurities (H and S) on the atomic, electronic structure, and mechanical properties of the γ-Fe Σ5 (021) grain boundary (GB) was investigated via first-principles calculations. H atoms act as an intergranular embrittler in the Σ5 GB due to a reduction in the charge density between the Fe atoms connected to the grains, whereas H and S co-segregation produces more pronounced embrittlement behavior, resulting in intergranular fracture. The S-induced embrittlement plays a crucial role in the H and S segregation, due to a combination of the structural and chemical effects. The fracturing of Σ5 GB due to S and H segregation is a two-step process. The first step is the breaking of Fe–Fe bonds in the GB, followed by the breaking of the remaining Fe–S bonds in the second step, resulting in the complete separation of the two grains. Moreover, the S atom can slightly compensate for the embrittlement induced by H, because some of the Fe atoms that obtain electrons from the S atoms can provide more electrons to the H atoms, and thus, they can compensate for the electrons that must be acquired from other Fe atoms. We call this “the electrons compensating effect” and this effect is helpful in the design and alloying of steels that are resistant to H embrittlement.     

Effect of 100 KeV Ar+ ion beam irradiation on ZnO thin films – Influence of morphology vis-a-vis electrode/electrolyte interface and its impact on photoelectrochemical water splitting

The present study attempts quantitative determination of changes in the morphological surface features viz. fractal dimension, lower and upper cut off length scale through Power Spectral Density analysis prior to and after irradiation of 100 KeV Ar⁺ ion beam at incidence angles of 0°, 40° and 60° on ZnO thin films. All the unirradiated and irradiated samples are subjected to photoelectrochemical characterization and a correlation between photoelectrochemical performance and morphological parameters is established. Sample irradiated at 40° angle at the fluence of 5 × 10¹⁶ ions/cm² is found to possess maximum fractal dimension of 2.72, lower and upper cut off length scale of 3.16 nm and 63.00 nm respectively. This sample exhibits maximum photocurrent density of 3.19 mA/cm² and applied bias photon-to-current efficiency of 1.12% at 1.23 V/RHE. Hydrogen gas collected for duration of 1 h for the same sample was ~4.83 mLcm^?2.     

Facile access to carboxyl-terminated polybutadiene and polyethylene from cis-polybutadiene rubber

Carboxyl-terminated polybutadiene (CTPB) is a widely used telechelic liquid rubber, which is mainly prepared by anionic or free-radical polymerization of 1,3-butadiene. It is known that the microstructure of liquid polybutadiene rubber largely affects its processability and mechanical properties. However, it is hard to control its microstructure in the free radical or anionic polymerization. In this study, a series of CTPB with high cis-1,4 content has been prepared for the first time via the oxidolysis and selective oxidation of cis-polybutadiene rubber (BR). Hydrogenation of their CC double bonds with p-toluenesulfonyl hydrazide/tri-n-propylamine (TSH/TPA) reagents afforded carboxyl-terminated polyethylenes (CTPE). For comparison, commercial CTPB (FCTPB), prepared by free-radical polymerization of 1,3-butadiene, was also hydrogenated and gave FCTPE with more ethyl branches. Linear CTPE (L-CTPE) was synthesized by ring-opening metathesis polymerization of 1,5-cyclooctadiene in the presence of maleic acid and subsequent hydrogenation. The microstructure of the polymers was established by FT-IR, ¹H NMR, ¹³C NMR, and GPC and their thermal properties were determined by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46934.     

Rational Designs for Lithium-Sulfur Batteries with Low Electrolyte/Sulfur Ratio

Lithium-sulfur batteries (LSBs) are considered a promising next-generation energy storage device owing to their high theoretical energy density. However, their overall performance is limited by several critical issues such as lithium polysulfide (PS) shuttles, low sulfur utilization, and unstable Li metal anodes. Despite recent huge progress, the electrolyte/sulfur ratio (E/S) used is usually very high (≥20 µL mg⁻¹), which greatly reduces the practical energy density of devices. To push forward LSBs from the lab to the industry, considerable attention is devoted to reducing E/S while ensuring the electrochemical performance. To date, however, few reviews have comprehensively elucidated the possible strategies to achieve that purpose. In this review, recent advances in low E/S cathodes and anodes based on the issues resulting from low E/S and the corresponding solutions are summarized. These will be beneficial for a systematic understanding of the rational design ideas and research trends of low E/S LSBs. In particular, three strategies are proposed for cathodes: preventing PS formation/aggregation to avoid inadequate dissolution, designing multifunctional macroporous networks to address incomplete infiltration, and utilizing an imprison strategy to relieve the adsorption dependence on specific surface area. Finally, the challenges and future prospects for low E/S LSBs are discussed.     

Remarkable Antibacterial Activity of Reduced Graphene Oxide Functionalized by Copper Ions

Despite long-term efforts for exploring antibacterial agents or drugs, potentiating antibacterial activity and meanwhile minimizing toxicity to the environment remains a challenge. Here, it is experimentally shown that the functionality of reduced graphene oxide (rGO) through copper ions displays selective antibacterial activity that is significantly stronger than that of rGO itself and no toxicity to mammalian cells. Remarkably, this antibacterial activity is two-orders-of-magnitude greater than the activity of its surrounding copper ions. It is demonstrated that rGO is functionalized through the cation–π interaction to massively adsorb copper ions to form a rGO–copper composite and result in an extremely low concentration level of surrounding copper ions (less than ≈0.5 µm ). These copper ions on rGO are positively charged and strongly interact with negatively charged bacterial cells to selectively achieve antibacterial activity, while rGO exhibits the functionality to not only actuate rapid delivery of copper ions and massive assembly onto bacterial cells but also result in the valence shift in the copper ions from Cu²⁺ into Cu⁺, which greatly enhances the antibacterial activity. Notably, this rGO functionality through cation–π interaction with copper ions can similarly achieve algaecidal activity but does not exert cytotoxicity against neutrally charged mammalian cells.