Cathodic electrosynthesis of iron oxide films for electrochemical supercapacitors

Cathodic electrosynthesis has been utilized for the fabrication of γ-Fe₂O₃ films, containing chitosan additive as a binder. The films were studied by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, differential thermal analysis, and thermogravimetric analysis. Cyclic voltammetry and chronopotentiometry data showed that the iron oxide films exhibit electrochemical capacitance in the voltage window of −0.9 to −0.1 V vs SCE in 0.25 m Na₂SO₄ and 0.25 m Na₂S₂O₃ aqueous solutions. The highest specific capacitance (SC) of 210 F g⁻¹ was achieved using 0.25 m Na₂S₂O₃ as electrolyte, at a scan rate of 2 mV s⁻¹. The SC decreased with increasing film thickness, scan rate and cycle number. Heat treatment of the films at 140 °C resulted in increasing SC.     

Synthetic diamond electrodes: The effect of surface microroughnesson the electrochemical properties of CVD diamond thin films on titanium

The electrochemical behavior of B-doped diamond films on Ti substrates subjected to different pretreatment procedures (annealing, sand-blasting, and etching in HCl) is evaluated as a function of surface microroughness. Generally, the differential capacitance follows the true surface area of the electrodes. The width of the potential window also increases, but slightly, with the roughness. The electrode reversibility in the [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ redox system increases with increasing surface roughness. The apparent increase in the reversibility of the reaction may be also explained by the decrease in the true current density. Although the variations in the electrochemical parameters are not strongly pronounced, the tendencies observed can be used to optimise the electrode properties.     

Electrodeposition and Capacitive Behavior of Films for Electrodes of Electrochemical Supercapacitors

Polypyrrole films were deposited by anodic electropolymerization on stainless steel substrates from aqueous pyrrole solutions containing sodium salicylate and tiron additives. The deposition yield was studied under galvanostatic conditions. The amount of the deposited material was varied by the variation of deposition time at a constant current density. SEM studies showed the formation of porous films with thicknesses in the range of 0–3 μm. Cyclic voltammetry data for the films tested in 0.5 M Na₂SO₄ solutions showed capacitive behavior and high specific capacitance (SC) in a voltage window of 0.9 V. The films prepared from pyrrole solutions containing tiron showed better capacitive behavior compared to the films prepared from the solutions containing sodium salicylate. A highest SC of 254 F g⁻¹ was observed for the sample with a specific mass of 89 μg cm⁻² at a scan rate of 2 mV s⁻¹. The SC decreased with an increasing film thickness and scan rate. The results indicated that the polypyrrole films deposited on the stainless steel substrates by anodic electropolymerization can be used as electrodes for electrochemical supercapacitors (ES).     

Electrochemical behavior of amorphous metal-silicon-carbon nanocomposites based on titanium or tungsten nanophase

Electrode behavior of nanocomposite films containing titanium- or tungsten-based conducting nanophase embedded in dielectric silicon-carbon matrix, deposited onto glassceramics substrate, is studied by cyclic voltammetry and electrochemical impedance spectroscopy. As the films’ resistivity decreases, their electrochemical behavior gradually changes from that of “poor conductor” to the nearly metal-like behavior. In particular, the differential capacitance increases, the charge transfer in a model redox system [Fe(CN)₆]^3−/4− accelerates, which may be explained by the increasing number of metal-containing clusters at the film/electrolyte solution interface.     

Voltammetric and electrochemical impedance spectroscopy characterization of a cathodic and anodic pre-treated boron doped diamond electrode

The effect of boron doped diamond (BDD) surface termination, immediately after cathodic and anodic electrochemical pre-treatments, on the electrochemical response of a BDD electrode in aqueous media and the influence of the different supporting electrolytes utilized in these pre-treatments on the final surface termination was investigated with [Fe(CN)₆]^4−/3−, as redox probe, by cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy. The cyclic voltammetry results indicate that the electrochemical behavior for the redox couple [Fe(CN)₆]^4−/3− is very dependent on the state of the BDD surface, and a reversible response was observed after the cathodic electrochemical pre-treatment, whereas a quasi-reversible response occurred after anodic electrochemical pre-treatment. Differential pulse voltammetry in acetate buffer also showed that the potential window is very much influenced by the electrochemical pre-treatment of the BDD surface. Electroactivity of non-diamond carbon surface species (sp² inclusions) incorporated into the diamond structure was observed after cathodic and anodic pre-treatments. Electrochemical impedance spectroscopy confirmed the cyclic voltammetry results and indicates that the BDD surface resistance and capacitance vary significantly with the electrolyte and with the electrochemical pre-treatment, caused by different surface terminations of the BDD electrode surface.     

Impact of electrolyte additives (alkali metal salts) on the capacitive behavior of NiO-based capacitors

To improve the specific capacitance and energy density of electrochemical capacitor, nanostructured NiO was prepared by high temperature solid-state method as electrode material. The crystal structure and morphology of as-parepared NiO samples were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Cyclic voltammetry (CV) measurement was applied to investigate the specific capacitance of the NiO electrode. Furthermore, a novel mixed electrolyte consisting of NaOH, KOH, LiOH and Li₂CO₃ was prepared for the NiO capacitor, and the component and concentration of the four different electrolytes was examined by orthogonal test. The results showed that the NiO sample has cubic structure with nano-size particles, and the optimal composition of the electrolyte was: NaOH 2 mol L⁻¹, KOH 3 mol L⁻¹, LiOH 0.05 mol L⁻¹, and Li₂CO₃ 0.05 mol L⁻¹. At a scan rate of 10 mV s⁻¹, the fabricated capacitor exhibits excellent electrochemical capacitive performance, while the specific capacitance and the energy density were 239 F g⁻¹ and 85 Wh kg⁻¹, which was higher than one-component electrolyte.     

Vacuum-annealed undoped polycrystalline CVD diamond: a new electrode material

Vacuum-annealing imparts conductivity to initially insulating undoped polycrystalline chemical-vapor-deposited diamond, thus turning it to a possible electrode material. The diamond film annealed at 1775 K appeared to be practically not conducting. With further increase in the annealing temperature above 1825 K, the film effective resistivity decreased from initial value of 10¹¹ to 10¹² Ω cm down to less than 0.1 Ω cm; the differential capacitance increased from ∼10⁻³ to ∼50 μF per 1 cm² of geometrical surface; the transfer coefficients for electrochemical reactions in the [Fe(CN)₆]^3−/4− redox solution increased from ∼0.2 to 0.5; and the degree of reversibility of the electrochemical reaction increased. The observed changes in the electrode properties are attributed to gradual change in the thickness and/or properties (first and foremost, conductivity) of the nondiamond carbon phase formed along the intercrystallite boundaries upon the annealing; the conducting phase is outcropping at the film surface as an array of microelectrodes (“active sites”).     

Characterization of boron-doped diamond electrodes by electrochemical impedance spectroscopy

Charge transfer on boron doped diamond (BDD) electrodes was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The diamond films of 5 μm thickness and boron content between 200 ppm and 3000 ppm were prepared by the hot filament CVD technique on niobium substrate and mounted in a Teflon holder as rotating disk electrodes. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na₂ SO ₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. Significant deviation in the redox behaviour of BDD and active Pt electrodes was indicated by a shift of the peak potentials in the cyclic voltammograms with increasing sweep rate and lower limiting diffusion current densities under rotating disk conditions. In the impedance spectra an additional capacitive element appeared at high frequencies. The potential and rotation dependence of the impedance spectra can be described quantitatively in terms of a model based on diffusion controlled charge transfer on partially blocked electrode surfaces. Direct evidence for the non-homogeneous current distribution on the diamond surface was obtained by SECM measurements.     

Electrochemical characteristics of boron doped polycrystalline diamond electrode sintered by high pressure and high temperature

The bulk B-doped polycrystalline diamond (PCD) electrode in this study was prepared by high-pressure, high-temperature (HPHT) technology. The PCD was sintered under HPHT conditions, using B-doped diamond powders and a metal catalyst as raw materials, then the metal solvent phase was dissolved by aqua regia. The morphology and composition of the PCD were investigated with a scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersion spectrum (EDS). The results show that the sintered body possesses a polycrystalline structure with direct diamond–diamond bond and irregularly shaped pores of 1–10 μm distributed on the grain boundaries after the metal solvent phase was removed. The cyclic voltammogram and electrochemical impedance spectroscopy of this B-doped electrode have been investigated. The B-doped PCD electrode exhibits stable electrochemistry in a KCl support solution over a wide potential range. The quasi-reversible reaction occurs on the electrode for the [Fe(CN)₆]^3−/4− couples. The electrode process combines the diffusion-controlled mass transport plus the kinetic process. The electrochemical impedance spectroscopy (EIS) analysis shows the porous structure characteristic of the PCD electrode.     

Capacitive behavior of polycarbazole- and poly(N-vinylcarbazole)-coated carbon fiber microelectrodes in various solutions

The electrochemical behavior of polycarbazole (PCz) and poly(N-vinyl carbazole) P(NVCz) was investigated by means of electrochemical impedance spectroscopy (EIS). Supporting electrolytes made from various combinations of solvents (acetonitrile and propylene carbonate) and salts (sodium perchlorate, lithium perchlorate, and tetraethyl ammonium perchlorate) were employed in the investigation. Information on the double layer capacitance (C_dl) and specific capacitance (C_sp) of P(NVCz) was achieved by cyclic voltammetry (CV), chronoamperometry and chronopotentiometry. Carbon fiber microelectrodes (CFME) were electrocoated by cyclic voltammetry in a monomer-free solution and displayed film thicknesses in the range ~200 nm to ~4.8 μm. The capacitive behavior of the PCz- and P(NVCz)-coated carbon fiber microelectrodes was also investigated by CV. The effects of the type of electrolyte and solvent on the electrochemical impedance spectroscopic data were subsequently fitted with an ((R(C(R(Q(RW))))(CR))-equivalent circuit model to calculate the numerical values of the proposed components. The obtained experimental C_sp values for PCz/CFME and P(NVCz)/CFME, as measured in LiClO₄/ACN, were 280.5 mF g⁻¹ and 294.1 mF g⁻¹, respectively.     

Effect of electrolyte concentration on morphology,microstructure and electrochemical impedance of anodic oxide film on titanium alloy Ti-10V–2Fe–3Al

Anodic oxide films were fabricated on titanium alloy Ti-10V–2Fe–3Al in ammonium tartrate solutions at the concentrations: 1, 3, 5, 10 and 15 g L⁻¹. The morphological characteristics and microstructures of the films of the alloy were studied by optical microscopy (OM) and Raman spectroscopy (Raman), respectively. The electrochemical impedances of the films in 0.5 mol L⁻¹ H₂SO₄ solution were investigated by electrochemical impedance spectroscopy (EIS). It was showed that different electrolyte concentrations led to different change rates of anodizing forming voltage. The change rate significantly affected the morphology, microstructure and electrochemical impedance of anodic oxide film. When electrolyte concentration was 5 g L⁻¹, anodic oxide film was the most uniform, exhibited by the least and smallest breakpoints on the film. In addition, the amount of crystal phase of the film was the largest at 5 g L⁻¹, showed by the highest intensity of Raman peaks. Furthermore, the electrochemical impedance of the film of the alloy was the greatest at 5 g L⁻¹, demonstrated by the highest values of polarization resistances and lowest values of capacitances. These phenomenon were associated with the minimum value of the change rate of anodizing forming voltage at 5 g L⁻¹.     

Capacitance properties of electrochemically deposited polyazulene films

Polyazulene films formed by electrochemical oxidation of azulene have been studied as active components in electrochemical capacitors. The film shows reversible electrochemical behavior in the positive potential range and exhibits p-doping properties. The influence of film formation conditions on the films electrochemical properties has been investigated. A strong effect of solvent on the polyazulene deposition has been observed. The highest yield of film deposition was found for dichloromethane. Polyazulene films also exhibit stable voltammetric properties in aprotic solvents. The voltammetric response of the film is affected by the size of the anion of the supporting electrolyte. In solutions containing tetra(alkyl)ammonium perchlorates, tetrafluoroborates or hexafluorophosphates, reversible oxidation of polyazulene is obtained. In the presence of large tetra(phenyl)borate anions, polyazulene is irreversibly oxidized upon electrochemical oxidation. The capacitance properties of these materials have been investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The polyazulene film displays a relatively high specific capacitance close to 400 F g⁻¹. Such high value of C_s locates this material among very good polymeric redox pseudo-capacitors.     

Supercapacitive behaviors of worm-like mesoporous carbon in non-aqueous electrolyte

This paper discusses the electrochemical behaviors of worm-like mesoporous carbon obtained in 1.0 mol L⁻¹ LiClO₄/ethylene carbonate + dimethyl carbonate solution. The capacitance for nanoporous carbon system advances up to 147 F g⁻¹ and a wide voltage window (2.5 V) for three electrode system was achieved. The specific energy and specific power reach as high as 127.6 Wh kg⁻¹ and 5.0 kW kg⁻¹. These results show that worm-like mesoporous carbon can be used for high energy density and power density non-aqueous electrolyte supercapacitors.     

Morphology-dependent electrochemical supercapacitive characteristics of nanostructured manganese dioxide

The dependence on morphology of the supercapacitive characteristics of manganese dioxide nanospheres (NSs) and nanorods (NRs) was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and a series of electrochemical techniques. Because the nanosized pores in MnO₂ NSs resulted in high surface area, MnO₂ electrodes made of NSs had higher specific capacitance (SC) than those made of NRs at current densities less than 2.0 A g⁻¹. However, at current densities over 2.0 A g⁻¹, the power density of MnO₂ electrodes composed of NRs was better than that of NSs. The high surface area and nanosized pores in MnO₂ NSs increase the number of redox active sites, which leads to high specific capacitance. On the other hand, the small pore size in MnO₂ NSs restricts the rates of charge and discharge, thus limiting their power density.     

Electrochemical behavior of LiCoO2 in a saturated aqueous Li2SO4 solution

The electrochemical behavior of a commercial LiCoO₂ with spherical shape in a saturated Li₂SO₄ aqueous solution was investigated with cyclic voltammetry and electrochemical impedance spectroscopy. Three redox couples at E_SCE = 0.87/0.71, 0.95/0.90 and 1.06/1.01 V corresponding to those found at ELi/Li⁺=4.08/3.83, 4.13/4.03 and 4.21/4.14 V in organic electrolyte solutions were observed. The diffusion coefficient of lithium ions is 1.649 × 10⁻¹⁰ cm² s⁻¹, close to the value in organic electrolyte solutions. The results indicate that the intercalation and deintercalation behavior of lithium ions in the Li₂SO₄ solution is similar to that in the organic electrolyte solutions. However, due to the higher ionic conductivity of the aqueous solution, current response and reversibility of redox behavior in the aqueous solution are better than in the organic electrolyte solutions, suggesting that the aqueous solution is favorable for high rate capability. The charge transfer resistance, the exchange current and the capacitance of the double layer vary with the charge voltage during the deintercalation process. At the peak of the oxidation (0.87 V), the charge transfer resistance is the lowest. These fundamental results provide a good base for exploring new safe power sources for large scale energy storage.     

Tunable electrochemical properties of liquid phase deposited TiO2 films

Titanium dioxide (TiO₂) films on glassy carbon (GC) electrode surface were prepared by the liquid phase deposition (LPD) process for different deposition times. The morphological structure, interfacial property and electrocatalytic activity of as-prepared LPD TiO₂ films on GC surface were studied by field-emission scanning electron microscopy (FE-SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FE-SEM observation showed that the deposition time controlled the morphology of film on GC surface. With increasing deposition time, TiO₂ formed nanoparticles at the initial 5-h stage and compact thick films after 20 h. Due to the semiconducting properties of TiO₂, the LPD films inhibited the electron transfer process of [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ on GC by increasing the redox reaction peak potential separation of CV curve and electron transfer resistance of EIS. The inhibition was increased with TiO₂ film thickness. Nevertheless, the onset reduction potential of maleic acid decreased with increasing LPD TiO₂ film thickness while the cathodic and anodic currents increased, demonstrating the useful electrocatalytic activity of LPD TiO₂ films.     

The influence of nanocrystalline state of iron on the corrosion inhibitor behavior in aqueous solution

Effect of grain size reduction on the electrochemical and corrosion behavior of iron of different grain sizes (32–320 nm) produced by direct and pulsed current electrodeposition was characterized using Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The grain size of deposits was determined by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The most intensive first-order peak (110) of the XRD patterns was taken for detailed analysis using a Gaussian fitting curve. The electrochemical tests were carried out in electrolyte 30 mg L⁻¹ NaCl + 70 mg L⁻¹ Na₂SO₄ + 250 mg L⁻¹ NaNO₂ aqueous solution. It was found that the corrosion potential and corrosion current density significantly changed as the microstructure morphology was changed. Results obtained from electrochemical tests suggested that the inhibition effect and corrosion protection of sodium nitrite inhibitor in near-neutral aqueous solutions increased as the grain size decreased from submicrocrystalline to nanocrystalline. This was attributed to the excess free energy, and concomitantly the increased number of the active sites caused by higher grain boundary and triple junction content in the nanocrystalline surface, which provides sites for electrochemical activity, and effect of sodium nitrite, was more pronounced.     

A modified composite film electrode of polyoxometalate/carbon nanotubes and its electrocatalytic reduction

Keggin-type polyoxometalate (H₄SiMo₁₂O₄₀) and carbon nanotubes (CNTs) coated by poly(allylamine hydrochloride) (PAH) were alternately deposited on glassy carbon (GC) electrodes by an electrochemical growth method in acidic aqueous solution. The preparation of the film electrode was simple and convenient. Thus-prepared multilayer films and the electrochemical behavior of the composite film modified electrode were characterized by UV–vis spectroscopy and cyclic voltammetry. It was shown that the multilayer films are uniform and stable. The resulting multilayer film modified electrode behaves as an electrochemical sensor because of its low overpotential for the catalytic reduction of S₂O₈ ²⁻ and NO₂ ⁻ in acidic aqueous solution.     

Investigations under real operating conditions of the electrochemical promotion by O<Subscript>2</Subscript> temperature programmed desorption measurements

The origin of the electrochemical promotion of catalysis (EPOC) was investigated via oxygen temperature-programmed desorption (O₂-TPD) from a polycrystalline Pt film interfaced with YSZ. TPD experiments were carried out under operating conditions similar to those used for catalytic activity measurements. This study has clearly shown that an anodic current generates the migration of “backspillover” ionic oxygen species from YSZ toward the Pt surface. These ionic species act as promoters and enable the formation of weakly adsorbed oxygen species coming from the gas phase which are more reactive and thus responsible for the activity enhancement. The effect of polarization is to carry or to remove the promoting ionic species on the Pt surface. Therefore, electrochemical promotion of catalysis can be considered as an electrically controlled metal support interaction, where the support is an O²⁻ conducting solid electrolyte.     

Electrochemical recycling of cobalt from spent cathodes of lithium-ion batteries: its application as supercapacitor

The supercapacitive behavior of the metallic cobalt recycled from Li-ion batteries has been studied in this work. The reversibility of both redox process (Co^II/Co^III) and (Co^III/Co^IV) in KOH 6 mol L⁻¹ is very high and promising for capacitive applications in electrochemical devices. The specific capacitances calculated from cyclic voltammetry and electrochemical impedance spectroscopy show a good agreement, giving the value of 625 Fg⁻¹. The electrode morphology presents a high porosity, thus an electrical equivalent circuit composed of two parallel resistance and capacitance elements in series was proposed. The specific capacitance values calculated from charge/discharge curves at 0.23 and 2.3 mA/cm² are 601 and 384 Fg⁻¹, respectively. Thereby, it was observed that metallic cobalt recycled from ion-Li batteries is compatible with other supercapacitive materials. This shows that cobalt recycling from Li-ion batteries is economically and environmentally viable for application in supercapacitor devices.