Preparation and electrochemical capacitance performances of super-hydrophilic conducting polyaniline

Super-hydrophilic conducting polyaniline was prepared by surface modification of polyaniline using tetraethyl orthosilicate in water/ethanol solution, whereas its conductivity was 4.16 S cm⁻¹ at 25 °C. And its electrochemical capacitance performances as an electrode material were evaluated by the cyclic voltammetry and galvanostatic charge/discharge test in 0.1 M H₂SO₄ aqueous solution. Its initial specific capacitance was 500 F g⁻¹ at a constant current density of 1.5 A g⁻¹, and the capacitance still reached about 400 F g⁻¹ after 5000 consecutive cycles. Moreover, its capacitance retention ratio was circa 70% with the growth of current densities from 1.5 to 20 A g⁻¹, indicating excellent rate capability. It would be a promising electrode material for aqueous redox supercapacitors.     

Effect of NaI/I2 mediators on properties of PEO/LiAlO2 based all-solid-state supercapacitors

NaI/I₂ mediators and activated carbon were added into poly(ethylene oxide) (PEO)/lithium aluminate (LiAlO₂) electrolyte to fabricate composite electrodes. All solid-state supercapacitors were fabricated using the as prepared composite electrodes and a Nafion 117 membrane as a separator. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements were conducted to evaluate the electrochemical properties of the supercapacitors. With the addition of NaI/I₂ mediators, the specific capacitance increased by 27 folds up to 150 F g⁻¹. The specific capacitance increased with increases in the concentration of mediators in the electrodes. The addition of mediators also reduced the electrode resistance and rendered a higher electron transfer rate between mediator and mediator. The stability of the all-solid-state supercapacitor was tested over 2000 charge/discharge cycles.     

Supercapacitors incorporating hollow cobalt sulfide hexagonal nanosheets

We have prepared hollow cobalt sulfide (CoS) hexagonal nanosheets (HNSs) from Co(NO₃)₂ and thioacetamide in the presence of poly(vinylpyrrolidone) (PVP) at 100 °C under alkaline condition. The as-prepared hollow CoS HNSs have an average edge length ca. 110 ± 27 nm and an outer shell of 16 ± 4 nm in thickness from 500 counts. The CoS HNSs are deposited onto transparent fluorine-doped tin oxide (FTO) substrates through a drop-dry process to prepare two types of supercapacitors (SCs); high rate and large per-area capacitance. The electrolyte used in this study is KOH_(aq). The CoS HNSs (8 μg cm⁻²) electrodes exhibit excellent capacity properties, including high energy density (13.2 h kg⁻¹), power density (17.5 kW kg⁻¹), energy deliverable efficiency (81.3-85.3%), and stable cycle life (over 10,000 cycles) at a high discharge current density of 64.6 A g⁻¹. With their fast charging and discharging rates (<3 s), the CoS HNSs show characteristics of high-rate SCs. The CoS HNS SCs having high mass loading (9.7 mg cm⁻²) provide high per-area capacitance of 1.35 F cm⁻² and per-mass capacitance of 138 F g⁻¹, respectively, showing characteristics of SCs with large per-area capacitance. Our results have demonstrated the potential of the CoS HNS electrodes hold great practical potential in many fields such as automobile and computer industries.     

Pseudo-capacitance of composite electrode of ruthenium oxide with porous carbon in non-aqueous electrolyte containing imidazolium salt

Pseudo-capacitance of composite materials where ruthenium oxide particles are loaded on activated carbon has been evaluated in the electrolyte of 1-ethyl-3-methyl imidazolium tetrafluoroborate dissolved in acetonitrile. The composite materials prepared by conventional a sol-gel method have dispersed structure of ruthenium oxide particle of tens nanometer diameter on the surface of activated carbon. The extent of the pseudo-capacitance of the composite electrodes in the imidazolium salt electrolyte, estimated by the comparison of the capacitance per surface area of electrode in different non-aqueous electrolyte, is ca. 3-5 μF cm⁻² in addition to the double-layer capacitance of ca. 6 μF cm⁻², depending on the loading status of ruthenium oxide. The symmetric cell consisting of the composite electrode containing 18 wt% of ruthenium oxide and the imidazolium salt electrolyte provides cell capacitance based on the pseudo-capacitance by a constant-current test.     

A doped activated carbon prepared from polyaniline for high performance supercapacitors

A novel doped activated carbon has been prepared from H₂SO₄-doped polyaniline which is prepared by the oxypolymerization of aniline. The morphology, surface chemical composition and surface area of the carbon have been investigated by scanning electron microscope, X-ray photoelectron spectroscopy and Brunaner-Emmett-Teller measurement, respectively. Electrochemical properties of the doped activated carbon have been studied by cyclic voltammograms, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 6 mol l⁻¹ KOH. The specific capacitance of the carbon is as high as 235 F g⁻¹, the specific capacitance hardly decreases at a high current density 11 A g⁻¹ after 10,000 cycles, which indicates that the carbon possesses excellent cycle durability and may be a promising candidate for supercapacitors.     

Poly(3-methylthiophene)/MnO2 composite electrodes as electrochemical capacitors

Composite electrodes prepared by electrodeposition of manganese oxide on titanium substrates modified with poly(3-methylthiophene) (PMeT) were investigated and compared with Ti/MnO₂ electrodes. The polymer films were prepared by galvanostatic deposition at 2 mA cm⁻² with different deposition charges (250 and 1500 mC cm⁻²). The electrodes were characterized by cyclic voltammetry in 1 mol L⁻¹ Na₂SO₄ and by scanning electron microscopy. The results show a very significant improvement in the specific capacitance of the oxide due the presence of the polymer coating. For Ti/MnO₂ the specific capacitance was of 122 F g⁻¹, while Ti/PMeT₂₅₀/MnO₂ and Ti/PMeT₁₅₀₀/MnO₂ displayed values of 218 and 66 F g⁻¹, respectively. If only oxide mass is considered, the capacitances of the composite electrode increases to 381 and 153 F g⁻¹, respectively. The micrographs of samples show that the polymer coating leads to very significant changes in the morphology of the oxide deposit, which in consequence, generate the improvement observed in the charge storage property.     

Electrochemically synthesized nanocrystalline spinel thin film for high performance supercapacitor

Spinels are not known for their supercapacitive nature. Here, we have explored electrochemically synthesized nanostructured NiCo₂O₄ spinel thin-film electrode for electrochemical supercapacitors. The nanostructured NiCo₂O₄ spinel thin film exhibited a high specific capacitance value of 580 F g⁻¹ and an energy density of 32 Wh kg⁻¹ at the power density of 4 kW kg⁻¹, accompanying with good cyclic stability.     

Performance of mesoporous carbons derived from poly(vinyl alcohol) in electrochemical capacitors

The present work shows that mesoporous materials obtained by the carbonization of mixtures of poly(vinyl alcohol) with magnesium citrate are very promising candidates for electrodes in supercapacitors. Their high performance arises essentially from a double-layer mechanism through the extent of the total surface area and one obtains at low current density (1 mA cm⁻²) values as high as 180 F g⁻¹ in aqueous 2 M H₂SO₄ electrolyte and around 100 F g⁻¹ in 1 M (C₂H₅)₄NBF₄ in acetonitrile. Moreover, in most cases the specific capacitance is reduced only by 15% at 100 mA cm⁻², as opposed to many other types of carbons which display much higher reductions.     

Wide-temperature range operation supercapacitors from nanostructured activated carbon fabric

Electrochemical power sources that offer high energy and power densities and, can also withstand a harsh temperature range have become extremely desirable in applications ranging from civilian portable electronic devices to military weapons. In this report, we demonstrated a wide temperature withstanding supercapacitor which can be operated from 100 °C to −40 °C within a voltage window from −2 V to 2 V. The performance of the supercapacitor coin cells, assembled with nanostructured activated carbon fabric (ACF) as the electrode material and 1 M tetraethylammonium tetrafluoroborate (TEABF₄) in polypropylene carbonate (PC) solution as the electrolyte, was systematically studied within the set temperature window. The ACF supercapacitor yielded ideal rectangular shapes in cyclic voltammograms within 0-100 °C with an average mass capacitance of 90 F g⁻¹ and, 60 F g⁻¹ at −25 °C. The capacitance was still over 20 F g⁻¹ at the extremely low temperature of −40 °C. Another exciting feature of the ACF supercapacitors was that they resumed their room temperature capacitance when cooled from 100 °C and defrosted from −40 °C, demonstrating an excellent repeatability and stability. The charge-discharge behavior of the ACF supercapacitors showed long-cycle stability at extreme temperatures. These high electrochemical performances make this type of supercapacitors very promising in many practical applications.     

Aqueous dispersed conducting polyaniline nanofibers: Promising high specific capacity electrode materials for supercapacitor

Aqueous dispersed conducting polyaniline nanofiber, new electrode material for supercapacitor, is prepared employing acidic phosphate ester as dopant for nanofibrous polyaniline emeraldine base, which is synthesized by polymerization of aniline using ferric nitrate as oxidant through pseudo-high dilution technique. Highly crystalline and uniform polyaniline fibers with thin diameter of 17-26 nm are obtained, the film from which shows electrical conductivity of 32 S cm⁻¹. The thin nanofibrous polyaniline is used as electrode material for supercapacitor and its performance is evaluated in non-protonic solvent system. It shows a specific capacitance as high as 160 F g⁻¹ at discharge rate of 0.4 A g⁻¹ from −1 V to 1 V in 1 mol L⁻¹ tetraethylammonium tetrafluoroborate/propylene carbonate solution, and the discharge/charge efficiency reaches 92%, indicating that it possesses good electrochemical reversibility. The high capacitance can be attributed to its relatively high surface area of 70 m² g⁻¹, which is 3-5 times higher than spherical polyaniline or thick fiberous polyaniline, leading to high utilization of the electroactive materials.     

Preparation and characterization of carbonaceous materials containing nitrogen as electrochemical capacitor

Carbonaceous materials containing nitrogen (C/N materials) were prepared by a pyrolysis of 2,3,6,7-tetracyano-1,4,5,8-tetraazanaphthalene (CAN). A C/N material prepared by the pyrolysis of CAN at 1070 K (CAN-1070 K) had a C/N atomic ratio of 3.0 and a non-crystalline carbonaceous structure with a BET surface area of 880 m² g⁻¹. The material CAN-1070 K showed large capacitances of 160–180 F g⁻¹ and 110–120 F cm⁻³ in case of current density of 10 mA cm⁻² (2 A g⁻¹) by using three-electrode cell in 1 M H₂SO₄ aqueous solution, in comparison with that of activated carbon (160 F g⁻¹ and 55 F cm⁻³) having BET surface area of 2300 m² g⁻¹. ESCA study indicated that pyridinic and quarternary nitrogen atoms existed in the C/N materials, which could result in producing a pseudo-capacitance in addition to the electric double layer capacitance. Also introduction of nitrogen into the carbonaceous material could enhance the wettability of material, which might also improve the capacitance.     

Effect of Nafion on the preparation and capacitance performance of polyaniline

With manganese dioxide (MnO₂) as the oxidant, perfluorinated sulfonic acid ion exchange resin (Nafion) as the doping agent and emulsifier, Nafion doped polyaniline (PANI-Nafion) was prepared by emulsion polymerization method. Scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) were carried out to characterize the structure and morphology of PANI-Nafion. Symmetric redox supercapacitor was assembled with PANI-Nafion as active electrode material and 1.0 mol L⁻¹ H₂SO₄ aqueous solution as electrolyte. The electrochemical characteristics of these supercapacitors were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge tests. These results show that the diameter of PANI-Nafion nanofiber is about 30 ∼ 40 nm and the pores between PANI-Nafion composite materials are distributed uniformly. The specific capacitance of PANI-Nafion electrode is about 385.3 F g⁻¹, which is higher than that of undoped PANI (235.8 F g⁻¹). After 1000 charge/discharge cycles the specific capacitance of PANI-Nafion electrode is 272.4 F g⁻¹, its capacity retention is 70.7%, which is significantly better than that of PANI electrode materials.     

A novel synthesis of mesoporous carbon microspheres for supercapacitor electrodes

Mesoporous carbon microspheres (MCMs) with the diameters of 0.5-2.0 μm, main mesopore sizes of 2.6-4.0 nm and specific surface areas of 449-1212 m² g⁻¹ are synthesized by a novel hydrothermal emulsion-activated method. The typical MCMs as electrode materials have a specific capacitance of 157 F g⁻¹ at a high current density of 10.0 A g⁻¹ in 6 M KOH aqueous solution. The resultant MCMs electrode materials with high current charge and discharge capability in 6 M KOH aqueous solution provide important prospect for electrode materials in supercapacitors which could offer high power density for electric vehicles.     

Multilayered films of cobalt oxyhydroxide nanowires/manganese oxide nanosheets for electrochemical capacitor

Multilayered films of cobalt oxyhydroxide nanowires (CoOOHNW) and exfoliated manganese oxide nanosheet (MONS) are fabricated by potentiostatic deposition and electrostatic self-assembly on indium-tin oxide coated glass substrates. The morphology and chemical composition of these films are characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS) and the potential application as electrochemical supercapacitors are investigated using cyclic voltammetry and charge-discharge measurements. These ITO/CoOOHNW/MONS multilayered film electrodes exhibit excellent electrochemical capacitance properties, including high specific capacitance (507 F g⁻¹) and long cycling durability (less 2% capacity loss after 5000 charge/discharge cycles). These characteristics indicate that these newly developed films may find important application for electrochemical capacitors.     

Anodic deposition of porous RuO2 on stainless steel for supercapacitor studies at high current densities

Ruthenium dioxide is deposited on stainless steel (SS) substrate by galvanostatic oxidation of Ru³⁺. At high current densities employed for this purpose, there is oxidation of water to oxygen, which occurs in parallel with Ru³⁺ oxidation. The oxygen evolution consumes a major portion of the charge. The oxygen evolution generates a high porosity to RuO₂ films, which is evident from scanning electron microscopy studies. RuO₂ is identified by X-ray photoelectron spectroscopy. Cyclic voltammetry and galvanostatic charge–discharge cycling studies indicate that RuO₂/SS electrodes possess good capacitance properties. Specific capacitance of 276 F g⁻¹ is obtained at current densities as high as 20 mA cm⁻² (13.33 A g⁻¹). Porous nature of RuO₂ facilitates passing of high currents during charge–discharge cycling. RuO₂/SS electrodes are thus useful for high power supercapacitor applications.     

Supercapacitive properties of polyaniline/Nafion/hydrous RuO2 composite electrodes

Chemically prepared polyaniline is tested for its supercapacitive behaviour in an aqueous electrolyte of 1.0 M H₂SO₄. In order to improve the cycleability of the polyaniline electrode, it is made into a composite with Nafion. This composite electrode shows improved cycleability and higher specific capacitance compared with a pure polyaniline electrode. It is therefore used as a matrix for the electrochemical deposition of hydrous RuO₂. The resulting ternary composite electrode has a high specific capacitance of 475 F g⁻¹ at 100 mV s⁻¹ and 375 F g⁻¹ at 1000 mV s⁻¹ in the voltage range of −0.2 to 0.8 V versus Ag/AgCl. All three types of electrode are characterized by cyclic voltammetry and impedance anaylsis.     

Preparation and characterization of polypyrrole films for three-dimensional micro supercapacitor

As electro-active electrodes for supercapacitors, micro polypyrrole (PPy) films doping with ClO₄⁻ (PPyClO₄) and Cl⁻ (PPy_Cl) are prepared on Ni layers modified three-dimensional (3D) structures in Si substrates. The key process to fabricate the 3D structures is high-aspect-ratio deep reactive ion etching, which result in significant increase of available surface area. Homogeneous conformal Ni layers and PPy films are deposited on the 3D structures by electroless plating and electropolymerization, respectively. The supercapacitor properties of PPy films are investigated by using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge with three-electrode system in NaCl solution. It is shown that doping with ClO₄⁻ results in ideal supercapacitor behaviors with rectangle-like CV shapes at scan rates from 5 to 200 mV s⁻¹, linear galvanostatic charge/discharge curves at current loads from 0.5 to 2 mA and stable cyclic property. However, doping with Cl⁻ gives rise to non-ideal properties of supercapacitor. SEM of the PPyClO₄ shows that the surface of the PPyClO₄ electrode is smooth and the thickness of the PPyClO₄ film is about 2.5 μm. The geometric capacitance of PPyClO₄ is calculated as 0.030 F cm⁻² from CV at scan rate of 100 mV s⁻¹, 0.023 F cm⁻² from EIS and 0.027 F cm⁻² from galvanostatic discharge at 1 mA cm⁻² current density.     

Template-free prepared micro/nanostructured polypyrrole with ultrafast charging/discharging rate and long cycle life

A highly electroactive polypyrrole with hollow “horns” in micro/nanometers (h-PPy) is galvanostatically prepared by a template-free approach in p-toluenesulfonate alkaline solution. Its electrochemical capacitance properties are characterized to verify its promising applicability for supercapacitors. Besides its high specific surface area, h-PPy shows unexpectedly good ordering of molecular chain and great conjugation length, contributing to high ionic and electronic conductivity. These advantages lead to a remarkable specific capacitance of 400 F g⁻¹ and ultrafast charging/discharging capability with a specific capacitance of 274 F g⁻¹ at the charging/discharging time of even 0.4 s. Moreover, the micro/nanostructured hollow “horns”, which can tolerate the mechanical stress in charging/discharging process, significantly improve the cycle life of h-PPy so that the capacitance retains 90% after 100,000 continuous cycles. All of its distinguishing quality enable h-PPy to be an excellent active material of supercapacitors.     

Electrochemical properties of manganese oxide coated onto carbon nanotubes for energy-storage applications

Birnessite-type manganese dioxide (MnO₂) is coated uniformly on carbon nanotubes (CNTs) by employing a spontaneous direct redox reaction between the CNTs and permanganate ions (MnO₄⁻). The initial specific capacitance of the MnO₂/CNT nanocomposite in an organic electrolyte at a large current density of 1 A g⁻¹ is 250 F g⁻¹. This is equivalent to 139 mAh g⁻¹ based on the total weight of the electrode material that includes the electroactive material, conducting agent and binder. The specific capacitance of the MnO₂ in the MnO₂/CNT nanocomposite is as high as 580 F g⁻¹ (320 mAh g⁻¹), indicating excellent electrochemical utilization of the MnO₂. The addition of CNTs as a conducting agent improves the high-rate capability of the MnO₂/CNT nanocomposite considerably. The in situ X-ray absorption near-edge structure (XANES) shows improvement in the structural and electrochemical reversibility of the MnO₂/CNT nanocomposite after heat-treatment.