A high-performance asymmetric supercapacitor based on carbon and carbon–MnO2 nanofiber electrodes

An asymmetric supercapacitor with high energy and power densities has been fabricated using MnO₂/carbon nanofiber composites as positive electrode and activated carbon nanofibers as negative electrode in Na₂SO₄ aqueous electrolyte. Both electrode materials are freestanding in nature without any conductive additives or binders and exhibit outstanding electrochemical performances. The as-assembled asymmetric supercapacitor with optimal mass ratio can be operated reversibly over a wide voltage range of 0–2.0 V, and presents a maximum energy density of 30.6 Wh kg⁻¹, which is much higher than those of symmetric supercapacitors. Moreover, the supercapacitor exhibits excellent rate capability (high power density of 20.8 kW kg⁻¹ at 8.7 Wh kg⁻¹) and long-term cycling stability with only 6% loss of its initial capacitance after 5000 cycles. These attractive results make these freestanding materials promising for applications in aqueous electrolyte-based asymmetric supercapacitors with high energy and power densities delivery.     

Electrophoretic co-deposition of Bi2O3–multiwalled carbon nanotubes coating as supercapacitor electrode

Nafion is suggested as an efficient assistant in preparing supercapacitor by employing nanoparticles. In this work, using a bi-additive of 0.10-mM NaOH + 0.10 g L⁻¹ Nafion, Nafion-assisted electrophoretic co-deposition of Bi₂O₃–multiwalled carbon nanotubes (MWCNTs) coating is successfully realized in ethanol solvent. The capacitance performances of the electrophoretic coatings in 6.0-M KOH electrolyte are investigated by cyclic voltammetry and galvanostatic charge–discharge techniques. Comparing with Bi₂O₃ coating prepared with electrophoretic deposition (EPD) by employing other additive (such as polyethyleneimine), the Bi₂O₃ coating prepared by Nafion-assisted EPD shows a better capacitance performance. Benefiting from the improvement in coating conductivity caused by MWCNTs, with a small additional amount of 4.0 wt.%, the Bi₂O₃–MWCNTs coating exhibits an amazing 164% increase of mass-specific capacitance (473 F g⁻¹ at the current density of 1.0 A g⁻¹) in comparison with pure Bi₂O₃ coating (179 F g⁻¹ at the current density of 1.0 A g⁻¹). The cyclic stability test exhibits excellent capacitance retention of 88.7% over 3000 cycles at a constant current density of 10.0 A g⁻¹. This work combines the advantages of MWCNTs, Nafion, and EPD to provide a facile route for preparing Bi₂O₃-based coating as a high-performance supercapacitor electrode.     

Asymmetric supercapacitor based on novel coal fly ash derived metal–organic frameworks as positive electrode and its derived carbon as negative electrode

Journal of Applied Electrochemistry - The paper presents a comparative study between aluminum fumarate metal–organic framework (Al-FumMOF) and a novel coal fly ash derived aluminum MOF...     

Electrocatalytic oxidation of methanol on the nickel–cobalt modified glassy carbon electrode in alkaline medium

In this work, Ni–Co alloy coating on the surface of glassy carbon (GC) electrode was performed by cyclic voltammetry. The results showed that the deposition of Ni–Co is an anomalous process. The deposition bath was prepared according to the metal ion Ni/Co ratio of 4:1 using NiSO₄·7H₂O and CoSO₄·8H₂O, and the total concentration of all solutions was 40.0 mM. The pH of the bath solution was adjusted at 2.0 using boric acid at room temperature. The modified electrode was conditioned by potential recycling in a potential range of 100–700 mV (vs. Ag/AgCl) by cyclic voltammetric method in an alkaline solution. The Ni–Co modified electrode showed a higher activity towards methanol oxidation in the Ni (III) and Co (IV) oxidation states. Cyclic voltammetry was used for the electrochemical characterization of the Ni–Co modified electrode and the mechanism of methanol oxidation is proposed. The result of double steps chronoamperometry shows that the methanol electrooxidation is an irreversible reaction. Moreover, the effects of various parameters such as mole ratio of Ni–Co in the alloy in modification step, potential scan rate, methanol concentration and solution temperature on the electro-oxidation of methanol have also been investigated.     

Electro-deposition and characterizations of nickel coatings on the carbon–polythene composite

Nickel coating on the carbon–polythene composite plate was prepared by electrodeposition in a nickel sulfate solution in this work. The morphology and cross-sectional microstructure of the nickel coating were examined by scanning electron microscope (SEM) and optical microscope (OM), respectively. The influence of bath temperature on the nickel deposition rate was investigated experimentally. The adhesion between the coating and the substrate was evaluated by the pull-off test. The corrosion behavior of the coating in an aqueous solution of NaCl was studied by electrochemical methods. The results showed that the nickel electrodeposition rate could reach up to 0.68 μm min⁻¹ on average under conditions of cathodic current density of 20 mA cm⁻² and bath temperature of 60 °C. It was confirmed that increasing the bath temperature up to 50 °C had a positive effect on the nickel deposit rate, while an adverse effect was observed beyond 60 °C. The adhesion strength between the nickel coating and the substrate can be more than 2.3 MPa. The corrosion potential of the bright coating in the NaCl solution was more positive than that of the dull coating, and the anodic dissolution rate of the bright coating was also far lower at the same polarization potential compared with the dull coating.     

Novel one-step synthesis for 3-D four-pointed micro-star of quaternary metal (Mo–V–Mn–Ag) oxide electrode for asymmetric supercapacitor

An intention of the present work is to synthesize a quaternary metal oxide by a simple and cost-effective method. MoVMnAg-oxide@Ni-foam is synthesised by one-step hydrothermal method. The as-deposited MoVMnAg-oxide sample is systematically examined through XRD, FESEM, EDS-mapping, and TEM analysis. The electrochemical performance of an MoVMnAg@Ni-foam electrode is tested using CV, GCD, and EIS techniques. MoVMnAg-oxide@Ni-foam has a considerable high areal capacitance of 651 mFcm^?2 with 0.13 mWhcm^?2 energy at 1.8 mWcm^?2 power density in 1 M KOH electrolyte calculated from GCD curves. Also, the electrode shows a diffusion coefficient of 1.52 × 10^?7 cm²s^?1 along with 91 % of diffusive-controlled contribution and a b-value of 0.51, which depicts faradaic charge storage mechanism. An assembled asymmetric supercapacitor device (MoVMnAg@Ni-foam//AC) delivers an areal capacitance of 312 mFcm^?2 with 0.37 mWcm^?2 power density at 1 mAcm^?2 current density within 0 – 1.5 V voltage window. The asymmetric device showed cyclability and coulombic efficiency of 80.3% and 95% respectively measured up to 10,000 GCD cycles. These results demonstrate the deposition of quaternary metal oxide directly on Ni-foam showing highly competitive electrochemical performance so that they can be utilized in energy storage applications.     

Carbon–carbon asymmetric aqueous capacitor by pseudocapacitive positive and stable negative electrodes

An asymmetric aqueous capacitor was constructed by employing zeolite-templated carbon (ZTC) as a pseudocapacitive positive electrode and KOH-activated carbon as a stable negative electrode. The asymmetric capacitor can be operated with the working voltage of 1.4 V, and exhibits an energy density that is comparable to those of conventional capacitors utilizing organic electrolytes, thanks to the large pseudocapacitance of ZTC. Despite relatively thick electrode (0.2 mm) configuration, the asymmetric capacitor could be well operated under a current density of 500 mA g⁻¹.     

Influence of quinone grafting via Friedel–Crafts reaction on carbon porous structure and supercapacitor performance

High specific surface area carbon has been modified with para-benzoquinone (p-BQ) via Friedel–Crafts reaction catalyzed by Iron(III) chloride followed by oxidation, in order to explore alternative strategies for obtaining high energy density supercapacitor materials by the combination of the double layer capacitance of carbons with the redox pseudocapacitance of the organic redox couple added on the carbon surface.Suitable structural and physicochemical characterization proved the formation of covalent bonds between carbon and p-BQ, and the electrochemical characterization showed a significant increase in gravimetric capacitance values after the addition of p-BQ which is maintained even after many cycles.This gravimetric capacitance increase was not only due to the redox reactions of p-BQ, but also to an increased double layer capacitance after p-BQ modification even when the BET surface area decreases after modification. A correlation with the pore structure of carbons showed that the increased double layer capacitance can be attributed to a better matching of carbon pore size with the size of electrolyte ions after p-BQ addition. Thus, this new addition strategy opens the way for the development of carbon-based materials for supercapacitors with higher energy densities coming from both increased pseudocapacitive reactions and increased double layer capacitance.     

Effect of fiber architecture and density on the ablation behavior of carbon/carbon composites modified by Zr–Ti–C

Three carbon/carbon (C/C) composites modified by Zr–Ti–C, with different fiber architecture in preforms and the same density, were prepared using chemical vapor infiltration and reactive melt infiltration methods. Two other samples with the same architecture in preforms and different density were also fabricated by the same methods. Their ablation behaviors were examined by oxy-acetylene flame. The results showed that the samples with chopped web needled perform had better ablation resistance than that of the samples with needle-integrated and fine-weave pierced perform. In the models of ablation behaviors, the sealing time of pores and gaps on the ablated surfaces has been defined to indirectly estimate the ablation property. The analysis of models also indicated that high density of the composites and appropriate small diameter of bundles of carbon fibers led to the short sealing time and good ablation resistance of the C/C–carbide composites.     

Bed density and circulation mass flowrate in a novel annulus-lifted gas–solid air loop reactor

Air loop reactors (ALR) have been widely used as promising and high-efficiency gas–liquid and gas–liquid–solid reactors. Extensive research on ALR has been conducted, but mostly limited to gas–liquid and gas–liquid–solid systems. Work associated with gas–solid systems has been rare and mainly focused on draft tube-lifted spouted bed treating coarse Geldart B, D particles. The present paper proposed a novel gas–solid air-loop reactor treating fine Geldart A particles and operating in a new annulus-lifted mode, with bubbling or turbulent bed upward flow in the annulus in parallel with bubbling bed downward flow in the draft tube. In view of these differences, distinct hydrodynamic behaviour can be anticipated for the gas–solid annulus-lifted air-loop reactor. The influence of operating conditions and geometric configuration on the distribution of bed density is discussed in a cold model annulus-lifted air loop reactor. A mechanistic model for the circulation mass flowrate is established based on an energy balance and resistance analysis. Nearly 50% and 30% of the energy dissipation rate occurs in the bottom and top regions, respectively. With increasing draft tube height, the energy dissipation rate increases in the annulus and draft tube regions, while it decreases in the top and bottom regions. The circulation mass flowrate decreases with increasing draft tube height. Analysis of the distribution of bed density and energy dissipation rate leads to suggestions regarding optimization of the design and axial location of the ring distributor and gap height.     

High butanol production by regulating carbon,redox and energy in Clostridia? ?

Butanol is a promising biofuel with high energy intensity and can be used as gasoline substitute. It can be produced as a sustainable energy by microorganisms (such as Clostridia) from low-value biomass. However, the low productivity, yield and selectivity in butanol fermentation are still big challenges due to the lack of an efficient butanol-producing host strain. In this article, we systematically review the host cell engineering of Clostridia, focusing on (1) various strategies to rebalance metabolic flux to achieve a high butanol production by regulating the metabolism of carbon, redox or energy, (2) the challenges in pathway manipulation, and (3) the application of proteomics technology to understand the intracellular metabolism. In addition, the process engineering is also briefly described. The objective of this review is to summarize the previous research achievements in the metabolic engineering of Clostridium and provide guidance for future novel strain construction to effectively produce butanol.     

The influence of polyaniline (PANI) coating on corrosion behaviour of zinc–cobalt coated carbon steel electrode

Zinc–cobalt alloy plating (ZnCo) was successfully deposited on carbon steel (CS) applying current of 2 mA with galvanostatic technique. Polyaniline film (PANI) was synthesized with cyclic voltammetry technique from 0.20 M aniline containing 0.20 M sodium tartrate solution on zinc–cobalt plated carbon steel (CS/ZnCo) electrode. PANI film characterized by scanning electron microscopy (SEM), was covered with a dark green-brown homopolymer film of strongly adherent homogeneous characteristic while the other one was plated with a porous light ZnCo one. The corrosion behaviour of zinc–cobalt deposited carbon steel electrodes with and without polyaniline (PANI) film in 3.5% NaCl solution was investigated with AC impedance spectroscopy (EIS) technique and anodic polarization curves. The results showed that PANI coating led to decrease of the permeability of metallic plating. The PANI homopolymer film provided an effective barrier property on zinc–cobalt coating and a remarkable anodic protection to substrate for longer exposure time.     

The high temperature reaction of ammonia with carbon and SiC–C ceramics

This contribution aimed at developing a treatment under ammonia in order to eliminate free carbon from the surface of SiC-based fine ceramics like fibers or coatings. The reaction of NH₃ with graphitic and non-graphitic carbon was first investigated through kinetic measurements, in situ gas phase analysis and physicochemical investigations of the solid. The carbon etching rate is controlled by heterogeneous reactions involving active sites arising from bulk structural defects and the formation of HCN. A selection of SiC-based fibers and coatings with various carbon contents and (micro)structures was treated in ammonia in favorable conditions. The analyses of the tested SiC–C specimens revealed a reduction of the free carbon content and, simultaneously, a nitridation of the initial Si–C–(O) continuum over a reaction layer. The growth rate, composition and the volume change of this layer vary with the initial microstructure. The ammonia treatment is able to restore the adhesion of carbon-contaminated surfaces.     

Preparation and electrochemical properties of SiO2–non-graphitizable carbon composites as negative electrode materials for Li-ion batteries

SiO₂–non-graphitizable carbon composites were prepared by pyrolysis of a mixture of ethyl cellulose and nano-sized SiO₂. The composite electrode showed high reversibility in insertion and/or extraction reactions of Li ions at potentials below 1 V with little hysteresis after the 2nd cycle, whereas a large irreversible capacity was observed in the 1st cycle. This reversible capacity increased with increasing SiO₂ content above 5 wt%. Li ion transfer at the interface between a composite electrode and an electrolyte was studied by ac impedance spectroscopy. In the Nyquist plots, a semi-circle that was assigned to charge-transfer resistance (R _ct) because of Li ion transfer across the interface between the composite electrode and electrolyte appeared at potentials below 1 V. The values of R _ct decreased with increasing SiO₂ content. These results indicate that both a decrease in R _ct and an increase in reversible capacity can be achieved by use of SiO₂–non-graphitizable carbon composite electrodes; this would lead to Li-ion batteries with higher power and energy density.     

Synthesis of a MnO2–graphene foam hybrid with controlled MnO2 particle shape and its use as a supercapacitor electrode

A simple approach was developed to synthesize the three-dimensional (3D) hybrid of manganese dioxide (MnO₂) and graphene foam. The morphology of the MnO₂ nanostructures can be readily controlled by the solution acidity. Furthermore, we demonstrate that, serving as a free-standing supercapacitor electrode, this novel three-dimensional hybrid gives a remarkable specific capacitance (560 F/g at the current density of 0.2 A/g) and excellent cycling stability.     

The effect of laser sintering on the microstructure,relative density,and cracking of sol-gel–derived silica thin films

Combining sol-gel processing and laser sintering is a promising way for fabricating functional ceramic deposition with high dimensional resolution. In this work, crack-free silica tracks on a silica substrate with a thickness from ~360 nm to ~950 nm, have been obtained by direct exposure to a CO₂ laser beam. At a fixed scanning speed, the density and microstructures of the silica deposition can be precisely controlled by varying the laser output power. The porosity of the laser-sintered silica tracks ranged from close to 0% to ~60%. When the thickness of the silica deposition exceeded the critical thickness (eg, ~2.2 µm before firing), cracks occurred in both laser-sintered and furnace-sintered samples. Cracks propagated along the edge of the laser-sintered track, resulting in the crack-free track. However, for the furnace heat-treated counterpart, the cracks spread randomly. To understand the laser sintering effect, we established a finite element model (FEM) to calculate the temperature profile of the substrate during laser scanning, which agreed well with the one-dimensional analytical model. The FEM model confirmed that laser sintering was the main thermal effect and the calculated temperature profile can be used to predict the microstructure of the laser-sintered tracks. Combining these results, we were able to fabricate, predesigned patterned (Clemson tiger paw) silica films with high density using a galvo scanner.