Electrosynthesis of Bi2O3 thin films and their use in electrochemical supercapacitors

Bismuth oxide (Bi₂O₃) thin films are grown on copper substrates at room temperature by electrodeposition from an aqueous alkaline nitrate bath. The usefulness of electrochemically deposited Bi₂O₃ for electrochemical supercapacitors is proposed for the first time. The supercapacitor properties of Bi₂O₃ electrode are studied in aqueous NaOH solution. The Bi₂O₃ electrode exhibits very good electrochemical supercapacitive characteristics as well as stability in aqueous NaOH electrolyte. The effect of electrolyte concentration, scan rate, and number of cycles on the specific capacitance of Bi₂O₃ electrodes has been studied. The highest specific capacitance achieved with the electrodeposited Bi₂O₃ films is 98 F g⁻¹.     

Porous structured vanadium oxide electrode material for electrochemical capacitors

A nano porous vanadium oxide (V₂O₅) was prepared by sol–gel method. The preparation involved elutriation of aqueous sodium meta vanadate over a cation exchange resin. The product was characterized using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, surface area analysis and thermogravimetric analysis. Electrochemical characterization was done using cyclic voltammetry in a three electrode system consisting of a saturated calomel electrode as reference electrode, platinum mesh as a counter electrode, and V₂O₅ mounted on Ti mesh as the working electrode. Two molars of aqueous KCl, NaCl and LiCl were used as electrolytes. A maximum capacitance of 214 F g⁻¹ was obtained at a scan rate of 5 mV s⁻¹ in 2 M KCl. The effect of different electrolytes and the effect of concentration of KCl on the specific capacitance of V₂O₅ were studied. Specific capacitance faded rapidly over 100 cycles in 2 M KCl at a 5 mV s⁻¹ scan rate.     

Electrochemical characterization on MnFe2O4/carbon black composite aqueous supercapacitors

MnFe₂O₄–carbon black (CB) composite powders synthesized by a co-precipitation method have been characterized and optimized for their electrochemical properties for supercapacitor applications. The composite shows pseudocapacitance in electrolyte solutions of alkali and alkaline chlorides, sulfates and sulfites. For the chlorides and sulfates electrolytes, the pseudocapacitance has been identified, by in situ X-ray absorption near-edge spectroscopy study, to involve charge-transfer at both the Mn and Fe sites of the ferrite. In 1 M NaCl_(aq), the composite electrode exhibits an operating potential window of 1.0 V with a maximum leakage current of 0.3 mA F⁻¹, and it exhibits far superior cycling stability to amorphous MnO₂ electrode. Both the specific capacitance and self-discharge behavior of the composite electrode depend strongly on the composite composition. The optimum capacitance occurs at ferrite:CB weight ratio of 7:3, which gives reduced self-discharge rate as compared with CB. The composite electrode also demonstrates capability of high-power delivery.     

Novel organic–inorganic poly (3,4-ethylenedioxythiophene) based nanohybrid materials for rechargeable lithium batteries and supercapacitors

Synthesis and characterization of poly (3,4-ethylenedioxythiophene) (PEDOT) interleaved between the layers of crystalline oxides of V and Mo is discussed with special emphasis on their application potential as electrodes for rechargeable Li batteries and supercapacitors. The expansion of the interlayer spacing of crystalline oxides (for example, V₂O₅ causes expansion from 0.43 to 1.41 nm) is consistent with a random layer stacking structure. These hybrid nanocomposites when coupled with a large-area Li foil electrode in 1 M LiClO₄ in a mixture of ethylene and dimethylcarbonate (1:1, v/v), give enhanced discharge capacity compared to pristine oxides. For example a discharge capacity of ∼350 mAh g⁻¹, in the potential range 4.2–2.1 V (versus Li⁺/Li) is obtained for PEDOT–V₂O₅ hybrid which is significantly large compared to that for simple Li-intercalated V₂O_5. The improvement of electrochemical performance compared with that of pristine oxides is attributed to higher electric conductivity, enhanced bi-dimensionality and increased structural disorder. Although these conducting polymer-oxide hybrids delivered more than 300 mAh g⁻¹ in the potential range 1.3–4.3 V, their cycle life needs further improvements to realize their commercial potential. Similarly, the double layer capacitance of MoO₃ increases from ∼40 mF g⁻¹ to ∼300 F g⁻¹ after PEDOT incorporation in the interlayer gap of MoO₃ under similar experimental conditions and the nanocomposite displays intriguing effects with respect to electrochemical Li⁺ insertion. The PEDOT–MoO₃ nanocomposite appears to be a promising electrode material for non-aqueous type supercapacitors.     

Preparation and optimization of RuO2-impregnated SnO2 xerogel supercapacitor

A Sb (6 mol%)-doped SnO₂ xerogel impregnated with RuO₂ nanocrystallites is prepared via an incipient-wetness method and is optimized for its electrochemical capacitance in aqueous 1 M KOH electrolyte by adjusting the calcination temperature and the RuO₂ loading. The electrode capacitance does not increase monotonically with increasing RuO₂ loading. A maximum electrode capacitance of 15 F g⁻¹, which represents a three-fold increase compared with the blank xerogel and a specific RuO₂ capacitance of 710 F g⁻¹ RuO₂, is obtained with a RuO₂ loading of 1.4 wt.% and by calcination at 200 °C. Higher loadings presumably result in a homogeneous nucleation upon drying, which causes severe reduction in the total surface area of the RuO₂ crystallites.     

Cresol–formaldehyde based carbon aerogel as electrode material for electrochemical capacitor

Carbon aerogels have been prepared through a polycondensation of cresol (Cm) with formaldehyde (F) and an ambient pressure drying followed by carbonization at 900 °C. Modification of the porous structures of the carbon aerogel can be achieved by CO₂ activation at various temperatures (800, 850, 900 °C) for 1–3 h. This process could be considered as an alternative economic route to the classic RF gels synthesis. The obtained carbon aerogels have been attempted as electrode materials in electric double-layer capacitors. The relevant electrochemical behaviors were characterized by constant current charge–discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy in an electrolyte of 30% KOH aqueous solution. The results indicate that a mass specific capacitance of up to 78 F g⁻¹ for the non-activated aerogel can be obtained at current density 1 mA cm⁻². CO₂ activation can effectively improve the specific capacitance of the carbon aerogel. After CO₂ activation performed at 900 °C for 2 h, the specific capacitance increases to 146 F g⁻¹ at the same current. Only a slight decrease in capacitance, from 146 to 131 F g⁻¹, was observed when the current density increases from 1 to 20 mA cm⁻², indicating a stable electrochemical property of carbon aerogel electrodes in 30% KOH aqueous electrolyte with various currents.     

Novel architecture of composite electrode for optimization of lithium battery performance

We show that the polymeric binder of the composite electrode may have an important role on the lithium trivanadate Li_1.2V₃O₈ electrode performance. We describe a new tailored polymeric binder combination with controlled polymer–filler (carbon black) interactions that allows the preparation of new and more efficient electrode architecture. Using this polymeric binder, composite electrodes based on Li_1.2V₃O₈ display a room temperature cycling capacity of 280 mAh g⁻¹ (C/5 rate, 3.3–2 V) instead of 150 mAh g⁻¹ using a standard-type (poly(vinylidene fluoride)–hexafluoropropylene (PVdF–HFP) binder) composite electrode. We have coupled scanning electron microscopy (SEM) observations, galvanostatic cycling and electrochemical impedance spectroscopy in order to define and understand the impact of the microstructure of the composite electrode on its electrochemical performance. Derived from these studies, the main key factors that provide efficient charge carrier collection within the composite electrode complex medium are discussed.     

Li+ ion diffusion in LiMn2O4 thin film prepared by PVP sol–gel method

LiMn₂O₄ thin film (1 μm thick) was prepared on a gold substrate by the PVP sol–gel method. The electrochemical properties of the thin-film electrode were studied in an electrolyte 1 mol dm⁻³ LiClO₄/(ethylene carbonate + diethyl carbonate). The prepared LiMn₂O₄ showed a good charge–discharge performance, and the capacity fade was ca. 20% during 200 cycles. The Li⁺ ion diffusion in the LiMn₂O₄ thin film was investigated by means of potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. The chemical diffusion coefficients were estimated to be 10⁻⁸ to 10⁻¹⁰ cm² s⁻¹.     

Performance investigations of Pb2Ru2O6.5 oxide based pseudocapacitors

Lead Pb/Ru pyrochlore (Pb₂Ru₂O_6.5) was synthesized as a new electrode material for aqueous-electrolyte capacitors. This material was characterized using X-ray diffraction, BET area anhgalysis and cyclic voltammetry. Small laboratory-scale prototype capacitors were fabricated with Pb₂Ru₂O_6.5 oxide electrodes and tested for their electrochemical performance in terms of capacitance, rate-capabilities, and energy–power performance. These laboratory cells exhibited excellent performance under constant power discharge delivering >5 W h/kg specific energy at 750 W/kg power level based on electrode and electrolyte masses only.     

Analysis of polyaniline-based nickel electrodes for electrochemical supercapacitors

Polyaniline is deposited potentiodynamically on a nickel substrate in the presence of p-toluene sulfonic acid and the specific capacitance is estimated. The electrochemical characterisation of the electrode is carried out by means of cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge experiments. The specific capacitance is ∼4.05 × 10² F g⁻¹. This indicates the feasibility of the polyaniline-coated nickel electrode for use in electrochemical supercapacitors.     

Synthesis and characterizations of Li[CrxLi(1−x)/3Mn2(1−x)/3]O2 (0.15 ≤ x ≤ 0.3) cathode materials in rechargeable lithium batteries

A series of Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ (0.15 ≤ x ≤ 0.3) cathode materials was prepared by citric acid-assisted, sol–gel process. Sub-micron sized particles were obtained and the X-ray diffraction (XRD) results showed that the crystal structure was similar to layered lithium transition metal oxides (R-3m space group). The electrochemical performance of the cathodes was evaluated over the voltage range 2.0–4.9 V at a current density of 7.947 mA g⁻¹. The Li_1.27Cr_0.2Mn_0.53O₂ electrode delivered a high reversible capacity of up to 280 mAh g⁻¹ during cycling. Li[Cr_xLi_(1−x)/3Mn_2(1−x)/3]O₂ yielded a promising cathode material.     

Evaluation of nafion based double layer capacitors by electrochemical impedance spectroscopy

In this work some electrochemical characteristics of all solid double layer capacitors prepared by high surface carbon and Nafion polymer electrolyte are reported. Carbon composite electrodes with a Nafion loading of 30 wt.% were prepared and evaluated. Nafion 115 membrane, recast Nafion membrane and 1 M H₂SO₄ solution in a matrix of glass fiber have been used as electrolyte, in the double layer capacitors. The different double layer capacitors (DLCs) have been evaluated by electrochemical impedance spectroscopy. The capacitor with a recast Nafion electrolyte exhibits a proton conductivity of about 3×10⁻² S cm⁻¹ at ambient temperature, that is higher of that reported for solid electrolytes (10⁻³ to 10⁻⁴ S cm⁻¹) in the current literature on capacitors. A maximum of specific capacitance of 13 F/g of active materials (carbon+Nafion) corresponding to 52 F/g for a single electrode measured in a three-electrode arrangement has been achieved with the capacitor with recast Nafion. The capacitance of the capacitor with recast Nafion electrolyte, evaluated in low-frequency region below 10 mHz, was practically equivalent at that with sulphuric acid electrolyte. The interpretation of the characteristics of the microporous structure of carbon material of the electrodes by impedance analysis is also discussed.     

Morphology and electrochemical behaviour of ruthenium oxide thin film deposited on carbon paper

In order to improve the efficiency of ruthenium dioxide, RuO₂, as an electrochemical capacitor electrode, a RuO₂ thin film is deposited on carbon paper and its structure and properties are evaluated. This new composite material is prepared via solution dip-coating of a Ru-ethoxide precursor and heat conversion. The coating thickness is easily controlled by varying the number of repetitions of the preparation process. The resulting structure consists of a by homogeneously coated RuO₂ film on carbon paper which has a porous graphite matrix. Extensive electrochemical studies have been performed in 1 M H₂SO₄ electrolyte in order to evaluate the properties of the composite as an electrode in an electrochemical capacitor. The composite material shows not only high specific capacitance (620 F g⁻¹) but also good power characteristics.     

Manganese oxide film electrodes prepared by electrostatic spray deposition for electrochemical capacitors from the KMnO4 solution

Manganese oxide film electrodes for electrochemical capacitors were deposited on the polished Pt foils by electrostatic spray deposition (ESD) from KMnO₄ precursor solution. The electrochemical properties of electrodes were systematically studied using cyclic voltammetry (CV), constant current charge–discharge tests, and electrochemical impedance spectroscopy (EIS). The specific capacitance (SC) of thick deposited film was 149 F g⁻¹ at the very high scan rate of 500 mV s⁻¹, in comparison with 209 F g⁻¹ at the low scan rate of 5 mV s⁻¹. The electrode shows good cyclic performance. The initial SC value was 163 F g⁻¹ and 103% of the initial SC can be retained after 10,000 cycles at the scan rate of 50 mV s⁻¹.     

Electrodeposition synthesis and electrochemical properties of nanostructured γ-MnO2 films

The thin films of carambola-like γ-MnO₂ nanoflakes with about 20 nm in thickness and at least 200 nm in width were prepared on nickel sheets by combination of potentiostatic and cyclic voltammetric electrodeposition techniques. The as-prepared MnO₂ nanomaterials, which were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), were used as the active material of the positive electrode for primary alkaline Zn/MnO₂ batteries and electrochemical supercapacitors. Electrochemical measurements showed that the MnO₂ nanoflake films displayed high potential plateau (around 1.0 V versus Zn) in primary Zn/MnO₂ batteries at the discharge current density of 500 mA g⁻¹ and high specific capacitance of 240 F g⁻¹ at the current density of 1 mA cm⁻². This indicated the potential application of carambola-like γ-MnO₂ nanoflakes in high-power batteries and electrochemical supercapacitors. The growth process for the one- and three-dimensional nanostructured MnO₂ was discussed on the basis of potentiostatic and cyclic voltammetric techniques. The present synthesis method can be extended to the preparation of other nanostructured metal-oxide films.     

Electrochemical capacitance of nanocomposite films formed by loading carbon nanotubes with ruthenium oxide

This work reports the supercapacitive properties of composite films of multiwalled carbon nanotubes (MWNT) and ruthenium oxide (RuO₂). Transmission and scanning electron microscopy, cyclic voltammetry, and electrochemical studies revealed that the nanoporous three-dimensional arrangement of RuO₂-coated MWNT in these films facilitated the improvement of electron and ion transfer relative to MWNT films. The capacitance was measured for films of different RuO₂ loading, revealing specific capacitances per mass as high as 628 F g⁻¹. The energy storage density of the electrode has increased about three times as compared to MWNT treated with piranha solution.     

Effects of electrolytes and electrochemical pretreatments on the capacitive characteristics of activated carbon fabrics for supercapacitors

The capacitive characteristics of activated carbon fabrics (ACFs) coated on the graphite substrates were systematically investigated by means of cyclic voltammetry and the galvanostatic charge–discharge technique. Effects of the PVDF contents in the electronically conductive binder, electrochemical pretreatments, and the electrolytes on the capacitive performance of ACFs were compared in aqueous media. These ACF-pasted electrodes showed the more ideally capacitive responses in 1 M NaNO₃ with a specific capacitance of 76 F g⁻¹ when the electronically conductive binder contained 40 wt.% PVDF. The specific capacitance of ACF-pasted electrodes reached a maximum in 0.5 M H₂SO₄ (about 153 F g⁻¹ measured at 25 mV s⁻¹), due to the presence of a suitable density of oxygen-containing functional groups, when they were subjected to the potentiostatic polarization at 1.8 V (versus reversible hydrogen electrode (RHE)) or potentio-dynamic polarization between 1.3 and 1.8 V in NaNO₃ for 20 min. The oxygen-containing functional groups within the electrochemically pretreated ACFs were identified by means of X-ray photoelectron spectroscopy (XPS).     

Symmetric redox supercapacitor with conducting polyaniline electrodes

Polyaniline doped with HCl (Pani-HCl) and LiPF₆ (Pani-LiPF₆) are prepared and used as the active electrode material of symmetric redox supercapacitors. The system using Et₄NBF₄ as an electrolyte solution has lower internal resistance and larger specific discharge capacitance, and thus, it is suitable for use in a polyaniline redox supercapacitor. The capacitance of Pani-HCl decreases during ∼400 cycles and then becomes constant at ∼40 F g⁻¹. On the other hand, the polyaniline electrode doped with lithium salt like LiPF₆ shows a specific discharge capacitance of ∼107 F g⁻¹ initially and ∼84 F g⁻¹ at 9000 cycles.     

Large scale hydrothermal synthesis and electrochemistry of ammonium vanadium bronze nanobelts

Single crystalline ammonium vanadium oxide bronze NH₄V₄O₁₀ nanobelts were synthesized by the hydrothermal treatment of H₂C₂O₄·2H₂O and NH₄VO₃ at 140 °C for 48 h. The NH₄V₄O₁₀ nanobelts were characterized using a combination of techniques including X-ray diffraction, transmission electron microscopy, selected area electronic diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy techniques. The as-obtained nanobelts are several microns long, typically 30–40 nm wide, and 10–20 nm thick. The electrochemical properties of the nanobelts were tested in cells with metallic lithium as the negative electrode, the first discharge capacity of 171.8 mAh g⁻¹ was achieved.     

Electrochemical profile of nano-particle CoAl double hydroxide/active carbon supercapacitor using KOH electrolyte solution

A nano-structured CoAl double hydroxide with an average particle size of 60–70 nm was prepared by a chemical co-precipitation. It was used as a positive electrode for the asymmetric hybrid supercapacitor in combination with an active carbon negative electrode in KOH electrolyte solution. The electrochemical capacitance performance of this kind of hybrid supercapacitor was investigated by means of cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. A specific capacitance of 77 F g⁻¹ with a specific energy density of 15.5 wh kg⁻¹ was obtained for the hybrid supercapacitor within the voltage range of 0.9–1.5 V. The supercapacitor also exhibits a good cycling performance and keep 90% of initial capacity over 1000 cycles.