Fabrication of different conductive matrix supported binary metal oxides for supercapacitors applications

Here, we have fabricated the spinel binary-metal oxide (FeCo₂O₄) via a solvent-free and cost-effective approach. The nanocomposites of the as-fabricated binary-metal spinel oxide have been prepared with three different conductive-matrices, namely r-GO, CNTs, and PANI, via ultra-sonication approach. The spinel phase and surface functionalities of the fabricated FeCo₂O₄ sample have been confirmed via XRD and FT-IR analyses, respectively. The morphological-structure and elemental composition of the fabricated samples have been probed via FESEM and EDX results. The role of added conductive-matrices in the improvement of the electrical conductivities of the fabricated nanocomposites has been investigated via I–V experiments. The electrochemical experiments, conducted in half-cell configuration, showed that FeCo₂O₄/PANI nanocomposite exhibited the highest specific capacitance (658.9 Fg^-1) than that of the remaining two nanocomposites. Furthermore, FeCo₂O₄/PANI nanocomposite exhibited excellent cyclic stability as it lost just 8.3% of its initial specific capacitance even after 3000 cyclic tests. The superior capacitive-activity of the FeCo₂O₄/PANI nanocomposite is accredited to its high conductivity, large surface area, and synergy effects between the pseudocapacitance derived from the PANI and FeCo₂O₄ nanostructure. The electrochemical and electrical measurements suggested that FeCo₂O₄/PANI nanostructure is an emerging contender for energy storage applications.     

Tailoring surface capacitance of Ti3C2Tx-PANI@CNTs nanoarchitecture for tunable energy storage and high-performance micro-supercapacitor

Transition metal carbide or nitride (MXenes), as a novel family of two-dimensional materials, exhibit huge potential for electrochemical energy storage thanks to their excellent electrical conductivity, fast ion diffusion rate, high electrochemical activity and good hydrophilicity. However, the electrochemical properties of MXenes tend to be deteriorated due to the self-restacking phenomenon. Herein, by self-assembly, a unique three-dimensional (3D) Ti₃C₂T_x-PANI@CNTs (TPCs) nanoarchitecture was constructed. Through optimizing structures, the surface capacitance of TPCs can be tailored to tune energy storage. The optimal specific capacitance up to 431.9 F/g was achieved under 1 A/g. Further, the TPCs nanoarchitectures were prepared into self-standing films with excellent mechanical properties and micro-supercapacitors (MSCs) in various shapes were manufactured based on the film. The MSCs demonstrate competitive energy storage capacities, obtaining an areal capacitance of 78.2 mF/cm² and energy density of up to 2.72 μWh/cm², still maintain excellent performance under harsh bending. The strategy for constructing 3D nanoarchitectures and further manufacturing MSCs can inspire the design of novel electrode materials and devices to advance the development in the field of energy storage.     

Nitrogen-doped hierarchically porous carbon obtained via single step method for high performance supercapacitors

In the present work, nitrogen doped hierarchically activated porous carbon (APC) samples have been synthesized via single step scalable method using ethylene di-amine tetra acetic acid (EDTA) as precursor and KOH as activating agent. Activated porous carbons with different pore sizes have been developed by varying the activation temperature. SEM, TEM and SAXS analysis suggest that with variation of activation temperature, a hierarchical porous structure with interconnected meso-pore and micro pores has been achieved. The sufficiently high surface area of the synthesized materials provides active sites to enhance the diffusion of ions between the electrolyte and the carbon electrodes. The electrode prepared at 800 °C activated sample exhibited highest specific capacitance of 274 Fg^-1 in two electrode setup, at a current density of 0.1 Ag^-1 in 1 M aqueous H₂SO₄. Along with this, it showed maximum energy density of 9.5 Whkg^?1 at a power density of 64.5 Wkg^-1. The remarkable electrochemical performance reveals that the synthesized nitrogen doped activated carbon electrodes derived from EDTA can be tuned to have optimum pore structure and pore size distribution for better electrochemical performance, so it can be considered as a potential electrode material for applications in electrochemical energy storage.     

Analysis and proposition of limiting current density measurement protocol

Limiting current density at different temperatures, backpressures, and balance gases can be used to separate molecular diffusion resistance, Knudsen diffusion resistance and local transport resistance of membrane electrode assembly (MEA). However, the measurement of limiting current density has no unified protocol. The diverse choices in the literature, either in the control of current or voltage or in the atmosphere like relative humidity and O₂ concentrations, make it difficult to compare the results and identify the true bottleneck hindering the mass transport. In this work, the current-voltage curves obtained by current scanning/stepping and voltage scanning/stepping methods under dilute O₂ of different concentrations and a wide range of relative humidity were measured and analyzed systematically. It is found that the voltage stepping method is superior to the other three ways of control for the reliable determination of the limiting current density. Aided with simultaneous electrochemical impedance spectroscopy measurement, the limiting current density can be determined with pinpoint accuracy. When the limiting current density is just used to qualitatively evaluate different MEA, the voltage scanning method can be used instead for its high time efficiency. The selection of the atmosphere also plays an important role in suppressing the distortion from excessive water and reducing the spurious contribution from proton conduction resistance. It is found that O₂ concentrations at 0.5 vol% and relative humidity at 90% can give the best estimation of O₂ transport resistance in membrane electrode assembly.     

Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Microcrack healing in zirconia ceramics under a DC electric field/current

Flash event caused by a DC electric field/current was applied to the crack healing in 8 mol % Y₂O₃ stabilized cubic ZrO₂ polycrystals (8Y-CSZ). The flash event, which occurred by applying the DC power higher than a critical value of 100 mW/mm³, successfully healed the microcrack within several minutes without any healing agents at a furnace temperature of 800 °C. As compared to the healing treatment under static annealing, the healing phenomena were accelerated about 2 times under the flash treatment even at the same temperatures, suggesting that the enhanced healing phenomena cannot be explained only by the temperature effect. Since the rate of grain growth was accelerated under the flash treatment, the flash healing would be accelerated through the current-enhanced diffusional processes. This study shows for the first time that the flash event has a potential to apply to the crack healing process in the ceramic materials and composites.     

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.     

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.