Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Plumbene: A next generation hydrogen storage medium

Plumbene, a recently discovered 2D material, has been examined for hydrogen storage. First principles calculations have been performed to investigate the hydrogen adsorption on pristine plumbene monolayer. The hydrogen molecule prefers to adsorb on three adsorption sites, i.e. H (hollow-site), T (top-site) and B (bond-site), of plumbene surface with desired adsorption energy. The adsorption energy is highest (−149 meV) at hollow site and lowest (−104 meV) at bond site. One side hydrogen decorated plumbene exhibit 3.37 wt% Hydrogen Gravimetric Density (HGD). Whereas 6.74 wt% (HGD), with the average adsorption energy of −117 meV/H_2, has been achieved in both side hydrogen decorated plumbene monolayer. Applied electric field can effectively controls the adsorption and desorption processes. Positive electric field makes the adsorption strong while the negative electric field results in weakening of hydrogen adsorption. It means electric field act as a switch to store and release hydrogen with good control and usage selectivity. Present study reveals that the plumbene is a strong candidate for hydrogen storage to meet the desired target of HGD suggested by U.S. Department of Energy by the year 2021.     

FeOOH–CoS composite catalyst with high catalytic performances for oxygen evolution reaction at high current density

Water electrolysis is an efficient approach for high-purity hydrogen production. However, the anodic sluggish oxygen evolution reaction (OER) always needs high overpotential and thus brings about superfluous electricity cost of water electrolysis. Therefore, exploiting highly efficient OER electrocatalysts with small overpotential especially at high current density will undoubtedly boost the development of industrial water electrolysis. Herein, we used a simple hydrothermal method to prepare a novel FeOOH–CoS nanocomposite on nickel foam (NF). The as-prepared FeOOH–CoS/NF catalyst displays an excellent OER performance with extremely low overpotentials of 306 and 329 mV at 500 and 1000 mA cm⁻² in 1.0 M KOH, respectively. In addition, the FeOOH–CoS/NF catalyst can maintain excellent catalytic stability for more than 50 h, and the OER catalytic activity shows almost no attenuation no matter after 1000 repeated CV cycles or 50 h of stability test. The high catalytic activity and stability have exceeded most non-noble metal electrocatalysts reported in literature, which makes the FeOOH–CoS/NF composite catalyst have promising applications in the industrial water electrolysis.     

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.     

Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

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.