Fluorination effect of activated carbon electrodes on the electrochemical performance of electric double layer capacitors

The surface of phenol-based activated carbon (AC) was fluorinated at room temperature with different F₂:N₂ gas mixtures for use as an electrode material in an electric double-layer capacitor (EDLC). The effect of surface fluorination on EDLC electrochemical performance was investigated. The specific capacitance of the fluorinated AC-based EDLC was measured in a 1 M H₂SO₄ electrolyte, in which it was observed that the specific capacitances increased from 375 and 145 F g⁻¹ to 491 and 212 F g⁻¹ with the scan rates of 2 and 50 mV s⁻¹, respectively, in comparison to those of an unfluorinated AC-based EDLC when the fluorination process was optimized via 0.2 bar partial F₂ gas pressure. This enhancement in capacitance can be attributed to the synergistic effect of increased polarization on the AC surface, specific surface area, and micro and mesopore volumes, all of which were induced by the fluorination process. The observed increase in polarization was derived from a highly electronegative fluorine functional group that emerged due to the fluorination process. The increased surface area and pore volume of the AC was derived from the physical function of the fluorine functional group.     

A spherical harmonic transform spectral analysis of a localized surface plasmon on a gold nano shell

We perform a study of the localized surface plasmon (LSP) modes of a gold nano shell having a silica core by means of discrete dipole approximation (DDA) and spherical harmonics transform for selected wavelengths. We demonstrate an efficient solution for the near and intermediate field terms by the dyadic Green function approach and determine the optical extinction efficiency by the far field term. Using this approach, we combine the advantages of a spectral analysis along with a DDA flexibility to solve an arbitrary shaped model and demonstrate the LSP dominant mode wavelength dependency. Our approach provides a metric which may be used to quantify the effects of minor changes in the model structure, or the external dielectric environment, in optical experiments. © 2014 Wiley Periodicals, Inc.     

Electrodeposition of metal nanostructures by galvanic displacement powered with insoluble crystals of a ferrocene derivative.

The deposition of metal nanostructures (wires and particles) on a graphite surface from an aqueous electrolyte solution was induced by galvanic displacement, via the oxidation of insoluble crystals of a ferrocene derivative (either n-butyl ferrocene or decamethyl ferrocene) present on the same substrate. Micron-to-millimetre-scale crystallites of decamethyl ferrocene were deposited on the graphite surface by evaporation from a solution of a nonpolar solvent (1,2-dichloroethane). Immersion of this modified surface into a dilute solution of a metal ion (e.g., CuII, AgI, PdII, PtII and others) caused the deposition of metal nanoparticles at step edges present on the graphite surface. The reducing equivalents required for the metal deposition process are provided by oxidation of the ferrocene derivative on the surface, as directly evidenced by elemental analysis and chronoamperometric experimental data presented here.     

The electrochemical determination of phenolic derivates using multiple pulsed amperometry with graphite based electrodes

The electrochemical determinations of 4-chlorophenol (4-CP) and 4-nitrophenol (4-NP) by chronoamperometry (CA) and multiple pulsed amperometry (MPA) using expanded graphite-epoxy composite (EG-Epoxy) and rotating spectral graphite disc (SG) electrodes are reported. The electrochemical behaviours of both electrodes in the presence of organics informed about oxidation peak potential and the electrode fouling with organics concentration increasing. Setting up the oxidation peak potential as detection potential, only SG gave good electroanalytical performance using CA. However, by MPA applying both electrodes exhibited the capability to assess electrochemically and quantitatively the pollutants from aqueous solutions. UV spectrometric method detecting 4-CP and 4-NP at λ = 280 nm and λ = 398 nm wavelength, respectively was used for validation and parallel determinations.     

Transient finite element analysis of electric double layer using Nernst-Planck-Poisson equations with a modified Stern layer

A finite element implementation of the transient nonlinear Nernst-Planck-Poisson (NPP) and Nernst-Planck-Poisson-modified Stern (NPPMS) models is presented. The NPPMS model uses multipoint constraints to account for finite ion size, resulting in realistic ion concentrations even at high surface potential. The Poisson-Boltzmann equation is used to provide a limited check of the transient models for low surface potential and dilute bulk solutions. The effects of the surface potential and bulk molarity on the electric potential and ion concentrations as functions of space and time are studied. The ability of the models to predict realistic energy storage capacity is investigated. The predicted energy is much more sensitive to surface potential than to bulk solution molarity.     

Salient features of the electrical double layer structure on mechanically renewed gold-silver electrodes in aqueous solutions of a surface-inactive electrolyte

The behavior of electrodes, which are made of binary Au-Ag alloys (Ag content 1–15 at %) and renewed by mechanical cutting in aqueous solutions of sodium fluoride, is studied with the aid of cyclic voltammetry and impedance methods. It is established that, in the region of potentials corresponding to ideal polarizability, the differential capacitance of the electrical double layer rapidly changes with time elapsed after the renewal of the surface of the electrodes. The change in the capacitance is brought about by the exit of silver atoms into a surface layer. The implication is that silver is the surface-active component in these alloys. The rate of the surface segregation of silver atoms depends on the electrode potential. The segregation rate substantially increases upon going into the region that corresponds to positive charges of the silver electrode surface and to the beginning of adsorption of atomic oxygen on the electrode. Based on phenomenological models, a method for processing capacitance curves is realized, which links experimentally observed time effects to variations that occur in the surface composition, and assumptions concerning the mechanism of relaxation processes that are responsible for the observed time effects are put forth. Explicit data on the effect, which is exerted by mechanical renewal on the composition of the surface layer of Au-Ag alloys at different distances from the interface with a vacuum, are obtained with the aid of an x-ray photoelectron spectroscopy method. It is established that the surface layer (～0.5 nm) is enriched by silver atoms as compared with the alloy’s bulk.     

Fabrication and characterization of electrochemical double layer capacitors using ionic liquid-based gel polymer electrolyte with chemically treated activated charcoal electrodes

The present investigation deals with electrochemical double layer capacitors (EDLCs) made up of ionic liquid (IL)-based gel polymer electrolytes with chemically treated activated charcoal electrodes. The gel polymer electrolyte comprising of poly(vinylidine fluoride-co-hexafluropropylene) (PVdF-HFP)–1-ethyl-2,3-dimethyl-imidazolium-tetrafluroborate [EDiMIM][BF₄]–propylene carbonate (PC)–magnesium perchlorate (Mg(ClO₄)₂) exhibits the highest ionic conductivity of ~8.4?×?10^?3?S?cm^?1 at room temperature (~20 °C), showing good mechanical and dimensional stability, suitable for their application in EDLCs. Activation of charcoal was done by impregnation method using potassium hydroxide (KOH) as activating agent. Brunauer–Emmett–Teller (BET) studies reveal that the effective surface area of treated activated charcoal powder (1,515 m²?g^?1) increases by more than double-fold compared to the untreated one (721 m²?g^?1). Performance of EDLCs has been tested using cyclic voltammetry, impedance spectroscopy, and charge–discharge techniques. Analysis shows that chemically treated activated charcoal electrodes have almost triple times more capacitance values as compared to the untreated one.     

A Long‐Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution

In this paper, we report an advanced long‐life lithium ion battery, employing a Pyr₁₄TFSI‐LiTFSI non‐flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn‐C) nanocomposite anode, and a layered LiNi_1/3Co_1/3Mn_1/3O₂ (NMC) cathode. The IL‐based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel–Tammann–Fulcher (VTF) trend. Lithium half‐cells employing the Sn‐C anode and NMC cathode in the Pyr₁₄TFSI‐LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn‐C electrodes are combined into a cathode‐limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g^?1 and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL‐based lithium ion cells are suitable batteries for application in electric vehicles.     

Hierarchical dendritic gold microstructure-based aptasensor for ultrasensitive electrochemical detection of thrombin using functionalized mesoporous silica nanospheres as signal tags

A sensitive electrochemical approach for the detection of thrombin was designed by using densely packed hierarchical dendritic gold microstructures (HDGMs) with secondary and tertiary branches as matrices, and thionine-functionalized mesoporous silica nanospheres as signal tags. To prepare the signal tags, the positively charged thionine (as an indicator) was initially adsorbed onto the mesoporous silica nanoparticles (MSNs). Then [AuCl₄]⁻ ions were in situ reduced on the thionine-modified MSNs by ascorbic acid to construct nanogold-decorated MSNs (GMSNs). The formed GMSNs were employed as label of the aminated aptamers. The assay was carried out in PBS, pH 7.4 with a sandwich-type assay mode by using the assembled thionine in the GMSNs as indicators. Compared with the pure silica nanoparticles, mesoporous silica could provide a larger surface for the immobilization of biomolecules and improve the sensitivity of the aptasensor. Under optimal conditions, the electrochemical aptasensors exhibited a wide linear range from 0.001 to 600 ng mL⁻¹ (i.e. 0.03 pM to 0.018 μM thrombin) with a low detection limit (LOD) of 0.5 pg mL⁻¹ (≈15 fM) thrombin at 3σ. No obvious non-specific adsorption was observed during a series of analyses to detect target analyte. The precision, selectivity and stability of the aptasensors were acceptable. Importantly, the methodology was evaluated with thrombin spiked samples in blank fetal calf serum, and the recoveries were 94.2–112%, indicating an exciting potential for thrombin detection.     

瞬时离子释放扩散模型及熔盐电解固态WS_2制备纳米W的液相扩散研究

固态化合物熔盐电解冶金在21世纪初被提出后受到学术界和工业界的广泛关注.根据固态化合物电解的动态三相电化学界线模型,固态金属氧(硫)化物阴极在电解还原过程中,涉及O2?(S2?)在电解生成的多孔金属层中的液相扩散,但由于一直以来缺乏方便可靠的理论和实验方法,相关传质过程动力学的研究鲜有文献报道.本文引入多孔电极瞬时离子释放扩散模型,以粉末微腔电极为微型多孔电极,设计双电势阶跃实验研究了WS2在等摩尔比NaCl+KCl熔盐中电解时固态阴极中的液相扩散.实验结果与理论模型符合良好,973 K时,硫离子在孔隙率为69%的多孔金属钨层中的扩散系数为0.92×10?5 cm2/s,扩散活化能为53.4 kJ/mol.研究表明,二硫化钨在NaCl+KCl混盐体系中能够快速电解还原生成纳米金属钨,其中,S2?的扩散传质是整个电解过程的速度控制步骤.     

A sensitive electrochemical sensor for detection of rutin based on a gold nanocage‐modified electrode

In this article, an electrochemical sensor based on a gold nanocage (AuNC)‐modified carbon ionic liquid electrode (CILE) was fabricated and applied to the sensitive rutin determination. The presence of AuNCs on the electrode surface greatly improved the electrochemical performance of the working electrode due to its specific microstructure and high metal conductivity. Electrochemical behavior of rutin on AuNCs/CILE was studied using cyclic voltammetry and differential pulse voltammetry with the related electrochemical parameters calculated. Under the optimal experimental conditions, the oxidation peak current of rutin and its concentration had good linear relationship in the range from 4.0 × 10^?9 to 7.0 × 10^?4 mol/L with a low detection limit of 1.33 × 10^?9 mol/L (3σ). This fabricated AuNCs/CILE was applied to direct detection of the rutin concentration in drug samples with satisfactory results, showing the real application of AuNCs in the field of chemically modified electrodes.     

Glucose oxidase electrodes of a terpolymer poly(aniline-co-o-anisidine-co-o-toluidine) as biosensors

A simple technique is described for constructing a glucose sensor by the entrapment of glucose oxidase (GOD) in a poly (aniline-co-o-anisidine-co-o-toluidine) [P(A-co-o-A-co-o-T)] thin films, which were electrochemically deposited on a platinum plate in phosphate and acetate buffer. The maximum current response was observed for the said electrodes at pH 5.5 and potential 0.60 V (versus Ag/AgCl). The phosphate buffer gives high stability and fast response as compared to acetate buffer in amperometric measurements.     

A review on the development of a porous carbon-based as modeling materials for electric double layer capacitors

Carbon electrodes are a key factor for electric double layer capacitors (EDLCs). Carbon gels have high porosity with a controllable pore structure by changing synthesis conditions and modifying preparation processing to improve the electrochemical performance of EDLCs. This review summarizes the preparation of carbon gels and their derivatives, the criteria to synthesize high surface area in each process, the development by some carbon forms, and EDLC applications. Porous carbons are also prepared as model materials by concentrating on how pore structure increases electrochemical capacitance, such as electronic and ion resistance, the tortuosity of pore channel, suitable micropore and mesopore sizes, and mesopore size distribution. This review emphasizes the significance of pore structures as the key factor to allow for the design of suitable pore structures that are suitable as the carbon electrode for EDLCs.     

Structural Design and Synthesis of an SnO2@C@Co-NC Composite as a High-Performance Anode Material for Lithium-Ion Batteries

To overcome the drawbacks of the structural instability and poor conductivity of SnO₂-based anode materials, a hollow core–shell-structured SnO₂@C@Co-NC (NC=N-doped carbon) composite was designed and synthesized by employing the heteroatom-doping and multiconfinement strategies. This composite material showed a much-reduced resistance to charge transfer and excellent cycling performance compared to the bare SnO₂ nanoparticles and SnO₂@C composites. The doped heteroatoms and heterostructure boost the charge transfer, and the porous structure shortens the Li-ion diffusion pathway. Also, the volume expansion of SnO₂ NPs is accommodated by the hollow space and restricted by the multishell heteroatom-doped carbon framework. As a result, this structured anode material delivered a high initial capacity of 1559.1 mA h g⁻¹ at 50 mA g⁻¹ and an initial charge capacity of 627.2 mA h g⁻¹ at 500 mA g⁻¹. Moreover, the discharge capacity could be maintained at 410.8 mA h g⁻¹ after 500 cycles with an attenuation rate of only 0.069 % per cycle. This multiconfined SnO₂@C@Co-NC structure with superior energy density and durable lifespan is highly promising for the next-generation lithium-ion batteries.     

Facile Synthesis of Ag Nanocubes of 30 to 70 nm in Edge Length with CF3COOAg as a Precursor

This paper describes a new protocol to synthesize Ag nanocubes of 30 to 70 nm in edge length with the use of CF₃COOAg as a precursor to elemental silver. By adding a trace amount of NaSH and HCl to the polyol synthesis, Ag nanocubes were obtained with good quality, high reproducibility, and on a scale up to 0.19 g per batch for the 70 nm Ag nanocubes. The Ag nanocubes were found to grow in size at a controllable pace over the course of synthesis. The linear relationship between the edge length of the Ag nanocubes and the position of localized surface plasmon resonance (LSPR) peak provides a simple method for finely tuning and controlling the size of the Ag nanocubes by monitoring the UV/Vis spectra of the reaction at different times.     

Metal framework as a novel approach for the fabrication of electric double layer capacitor device with high energy density using plasticized Poly(vinyl alcohol): Ammonium thiocyanate based polymer electrolyte

High performance electric double-layer capacitors (EDLCs) based on poly (vinyl alcohol) (PVA): ammonium thiocyanate (NH₄SCN):Cu(II)-complex plasticized with glycerol (GLY) have been fabricated. The maximum DC ionic conductivity (σ_DC) of 2.25 × 10^-3 S cm⁻¹ is achieved at ambient temperature. The X-ray diffraction (XRD) patterns confirmed that the addition of both Cu(II)–complex and GLY enhanced the amorphous region within the samples. Through the Fourier transform infrared (FTIR) the interactions between the host polymer and other components of the prepared electrolyte are observed. The FESEM images reveal that the surface morphology of the samples showed a uniform smooth surface at high GLY concentration. This is in good agreement with the XRD and FTIR results. Transference numbers of ion (t_ion) and electron (t_el) for the highest conducting composite polymer electrolyte (CPE) are recognized to be 0.971 and 0.029, respectively. The linear sweep voltammetry (LSV) revealed that the electrochemical stability window for the CPE is 2.15 V. These high values of t_ion and potential stability established the suitability of the synthesized systems for EDLC application. Cyclic voltammetry (CV) offered nearly rectangular shape with the lack of Faradaic peak. The specific capacitance and energy density of the EDLC are nearly constant within 1000 cycles at a current density of 0.5 mA/cm² with average of 155.322F/g and 17.473 Wh/Kg, respectively. The energy density of the EDLC in the current work is in the range of battery specific energy. The EDLC performance was found to be stable over 1000 cycles. The low value of equivalent series resistance reveals that the EDLC has good electrolyte-electrode contact. The EDLC exhibited the initial high power density of 4.960 × 10³ W/Kg.