Influence of the mesoporous structure on capacitance of the RuO2 electrode

The difference in capacitive performance between high and low surface area RuO₂ electrodes, synthesized with and without a mesoporous silica template, respectively, was investigated in aqueous solutions of sulfuric acid and sulfates by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). RuO₂ synthesized with the template was crystalline and the formation of the mesoporous structure with a 6.5 nm diameter was confirmed using a transmission electron microscope and the nitrogen adsorption and desorption isotherm. From the CV at the scan rate of 1 mV s⁻¹, the specific capacitance of the high surface area electrode in H₂SO₄(aq) was determined to be 200 F g⁻¹. The high surface area RuO₂ has a three times higher BET specific surface area (140 m² g⁻¹) than the low surface area sample (39 m² g⁻¹). Introducing the mesoporous structure was proved effective for increasing the capacitance per mass of the RuO₂, though not all the surface functions as a capacitor. Both the CV and EIS suggest that by increasing the charging rate or frequency, the mesoporous structure of the electrode leads to a lower capacitance decrease (higher capacitance retention) than the low surface area electrode. The EIS also indicates that the response time of the capacitor is hardly influenced by the presence of the mesoporous structure.     

Carbon nanofibre/hydrous RuO2 nanocomposite electrodes for supercapacitors

Amorphous RuO₂·xH₂O and a VGCF/RuO₂·xH₂O nanocomposite (VGCF = vapour-grown carbon fibre) are prepared by thermal decomposition. The morphology of the materials is investigated by means of scanning electron microscopy. The electrochemical characteristics of the materials, such as specific capacitance and rate capability, are investigated by cyclic voltammetry over a voltage range of 0–1.0 V at various scan rates and with an electrolyte solution of 1.0 M H₂SO₄. The specific capacitance of RuO₂·xH₂O and VGCF/RuO₂·xH₂O nanocomposite electrodes at a scan rate of 10 mV s⁻¹ is 410 and 1017 F g⁻¹, respectively, and at 1000 mV s⁻¹ are 258 and 824 F g⁻¹, respectively. Measurements of ac impedance spectra are made on both the electrodes at various bias potentials to obtain a more detailed understanding of their electrochemical behaviour. Long-term cycle-life tests for 10⁴ cycles shows that the RuO₂·xH₂O and VGCF/RuO₂·xH₂O electrodes retain 90 and 97% capacity, respectively. These encouraging results warrant further development of these electrode materials towards practical application.     

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.     

Electrodeposition of mesoporous manganese dioxide supercapacitor electrodes through self-assembled triblock copolymer templates

Mesoporous manganese dioxide supercapcitor electrode materials were electrochemically deposited onto silicon substrates coated with Pt using triblock copolymer species (Pluronic P123 and F127) as the structure-directing agents. Deposited electrodes of manganese dioxide film were physically characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and were electrochemically characterized by cyclic voltammetry (CV) in 0.5 M Na₂SO₄ electrolyte. Maximum specific capacitance (SC) values of 449 F g⁻¹ was obtained at a scan rate of 10 mV s⁻¹ from F127 templated mesoporous MnO₂.     

Tailoring of RuO2 nanoparticles by microwave assisted “Instant method” for energy storage applications

RuO₂ nanoparticles are synthesized by Instant method using Li₂CO₃ as stabilizing agent, under microwave irradiation at 60 °C and investigated for the anodic oxygen evolution reaction (OER) and for their supercapacitance properties in 0.5 M H₂SO₄ medium. Structural and morphological characterizations of RuO₂ are investigated by in situ X-ray diffraction (XRD), thermogravimetric analysis (TG-DTA), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDS) and Raman spectroscopy. The TEM images of as prepared material show the uniform distribution of RuO₂ nanoparticles with mean diameter of ca. 1.5 nm. Analysis on as prepared material indicates the structural formula as [RuO₂·2.6H₂O] 0.7H₂O with low crystallinity. The influence of annealing temperature on RuO₂ is studied in light of electrocatalytic activity for oxygen evolution reaction (OER) and capacitance. Electrochemical performances of RuO₂ electrodes are followed by current-potential curves, galvanostatic charge-discharge cycles and evolved oxygen measurements. The amount of oxygen gas evolved during the OER by the crystalline RuO₂ is found to be consistent with the electrical energy supplied to the catalyst. The cyclic voltammogram of RuO₂ exhibits the typical capacitance behavior with highly reversible nature. The specific capacitance of hydrous RuO₂ is found to be 737 F g⁻¹ at the scan rate of 2 mV s⁻¹, by the balanced transport of proton through the structural water and electron transport along dioxo bridges, which makes a suitable material for energy storage. The specific capacitance decreases with increase in the crystallinity of RuO₂. The present study shows the potential method to synthesize rapid and uniform nano particles of RuO₂ for water electrolysis and supercapacitors.     

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.     

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.     

Biomolecule-assisted synthesis of cobalt sulfide nanowires for application in supercapacitors

A biomolecule-assisted hydrothermal process is developed to synthesize cobalt sulfide (CoS), in which l-cysteine is used as the sulfide source and directing molecule. By controlling the synthesis conditions, CoS nanospheres and nanowires can be assembled. The as-synthesized samples are characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) are used to study the effects of microstructure and morphology of the samples on their capacitance and conductivity. A specific capacitance, as high as 508 F g⁻¹, is achieved for CoS nanowires. This is very competitive with the best supercapacitor material, RuO₂ (720–760 F g⁻¹), but its cost is remarkably lower than RuO₂. Thus the nanowires are a promising material for low-cost, high-performance supercapacitors. This method could provide a universal green chemistry approach to synthesize other metal sulfides.     

Electrochemical supercapacitor behavior of Ni3(Fe(CN)6)2(H2O) nanoparticles

Nanosized Ni₃(Fe(CN)₆)₂(H₂O) was prepared by a simple co-precipitation method. The electrochemical properties of the sample as the electrode material for supercapacitor were studied by cyclic voltammetry (CV), constant charge/discharge tests and electrochemical impedance spectroscopy (EIS). A specific capacitance of 574.7 F g⁻¹ was obtained at the current density of 0.2 A g⁻¹ in the potential range from 0.3 V to 0.6 V in 1 M KNO₃ electrolyte. Approximately 87.46% of specific discharge capacitance was remained at the current density of 1.4 A g⁻¹ after 1000 cycles.     

Preparation of mesoporous carbons from amphiphilic carbonaceous material for high-performance electric double-layer capacitors

Amphiphilic carbonaceous material (ACM), with nanoscale dispersion in alkaline aqueous solutions, is synthesized from green needle coke. As a special precursor with small particle size, plenty of functional groups and widened d₀₀₂ simultaneously, ACM guarantees subsequent ACM-based activated carbons (AACs) with high specific surface area over 3000 m² g⁻¹ as well as well-developed mesoporous structure after KOH activation. Such pore properties enable AACs’ high performances as electrode materials for electric double-layer capacitors (EDLCs). In particular, surface area up to 3347 m² g⁻¹ together with notable mesopore proportion (26.9%) gives sample AAC814 outstanding EDLC behaviors during a series of electrochemical tests including galvanostatic charge/discharge, CV and electrochemical impedance spectroscopy. The electrode gets satisfactory gravimetric and volumetric specific capacitance at the current density of 50 mA g⁻¹, up to 348 F g⁻¹ and 162 F cm⁻³, respectively. Furthermore, for the mesoporosity, there is only a slight capacitance reduction for AAC814 as the current density reaches 1000 mA g⁻¹, indicating its good rate performance. It is all the ACM's unique characteristics that make AACs a sort of competitive EDLC electrode materials, both in terms of specific capacitance and rate capability.     

Facile synthesis and electrochemical properties of conducting SrRuO3-RuO2 composite nanofibre mats

This study reports the facile synthesis of highly conductive SrRuO₃(SRO)-RuO₂ composite nanofibre mats and their potential suitability for application in electrochemical capacitors as an active electrode material. SRO-RuO₂/poly(vinyl acetate) composite nanofibre mats are electrospun on to a Au-coated SiO₂/Si substrate and a Ti substrate, subsequently thermocompressed at 60 °C, and calcined at various temperatures (from 350 to 850 °C). The calcined SRO-RuO₂ nanofibre mats exhibit porous morphologies and bundle shapes composed of multiple-fibrils with a nanoparticle diameter ranging from 20 to 50 nm. Single SRO-RuO₂ nanofibre and multiple SRO-RuO₂ nanofibre mats show high electrical conductivity of 476 and 40.8 S cm⁻¹, respectively. Pseudocapacitors using SRO-RuO₂ nanofibre mats calcined at 350 °C exhibit a high specific capacitance of 192 F g⁻¹ at a scan rate of 10 mV s⁻¹. The superior capacitance retention (83.4%) of the SRO-RuO₂ nanofibre mats is maintained even at rapid scan rate of 1000 mV s⁻¹.     

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.     

Solid state synthesis of hydrous ruthenium oxide for supercapacitors

A novel solid state route has been successfully developed for the synthesis of nano-scale hydrous ruthenium oxide (denoted as RuO₂·xH₂O). The procedure involves directly mixing RuCl₂·xH₂O with alkali to form RuO₂·xH₂O in a mortar at room temperature. Transmission electron microscopy (TEM) and N₂ adsorption–desorption measurement indicate that the RuO₂·xH₂O particle is approximately 30–40 nm with mesoporous structure. The crystalline structure and the electrochemical properties of RuO₂·xH₂O have been systematically explored as a function of annealing temperature. At lower temperatures, the RuO₂·xH₂O powder was found in an amorphous phase and the maximum capacitance of 655 F g⁻¹ was obtained by annealing at 150 °C. Higher temperatures (exceeding 175 °C) presumably converted amorphous phase into crystalline one and the corresponding specific capacitance dropped rapidly from 547 F g⁻¹ at 175 °C to 87 F g⁻¹ at 400 °C. Also, the dependence of electrochemical performance on annealing conditions of RuO₂·xH₂O was investigated by electrical impedance spectroscopy (EIS) study.     

Cathodic deposition and characterization of tin oxide coatings on graphite for electrochemical supercapacitors

Amorphous tin oxide (SnO_x) was cathodically deposited onto graphite electrode in a bath containing 0.1 M stannous chloride (SnCl₂), 0.5 M sodium nitrate (NaNO₃), and 0.4 M nitric acid (HNO₃) in an aqueous solution of 50% (v/v) ethanol. The SnO_x coatings grown on graphite were characterized as typical capacitive behaviors by cyclic voltammetry (CV), chronopotentiometric (CP) in 0.5 M KCl. Specific capacitance (in milli-farad per square centimeter, C_a) changes linearly with the deposition charge up to 4.5 C cm⁻², and a maximum of as high as 355 mF cm⁻² was obtained with the SnO_x coating grown at around 5 C cm⁻². For the SnO_x coating deposited at 0.2 C cm⁻², a maximum specific capacitance (in farad per gram, C_m) of 298 and 125 F g⁻¹ was achieved from CVs at a scan rate of 10, and 200 mV s⁻¹, respectively. The value of C_m significantly gets lower from 265 to around 95 F g⁻¹ when the deposition charge increases from 0.2 to around 6.0 C cm⁻². The long cycle-life and stability of the SnO_x coatings on graphite via the presented cathodic deposition were also demonstrated.     

Symmetric redox supercapacitor based on micro-fabrication with three-dimensional polypyrrole electrodes

To achieve higher energy density and power density, we have designed and fabricated a symmetric redox supercapacitor based on microelectromechanical system (MEMS) technologies. The supercapacitor consists of a three-dimensional (3D) microstructure on silicon substrate micromachined by high-aspect-ratio deep reactive ion etching (DRIE) method, two sputtered Ti current collectors and two electrochemical polymerized polypyrrole (PPy) films as electrodes. Electrochemical tests, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatical charge/discharge methods have been carried out on the single PPy electrodes and the symmetric supercapacitor in different electrolytes. The specific capacitance (capacitance per unit footprint area) and specific power (power per unit footprint area) of the PPy electrodes and symmetric supercapacitor can be calculated from the electrochemical test data. It is found that NaCl solution is a good electrolyte for the polymerized PPy electrodes. In NaCl electrolyte, single PPy electrodes exhibit 0.128 F cm⁻² specific capacitance and 1.28 mW cm⁻² specific power at 20 mV s⁻¹ scan rate. The symmetric supercapacitor presents 0.056 F cm⁻² specific capacitance and 0.56 mW cm⁻² specific power at 20 mV s⁻¹ scan rate.     

Improved pseudocapacitive performance and cycle life of cobalt hydroxide on an electrochemically derived nano-porous Ni framework

The pseudocapacitance and morphology of an electrodeposited cobalt hydroxide (Co(OH)₂) significantly depends on the architecture of the electrode substrate. The nano-porous Ni framework, derived from the selective dissolution of Cu from a Ni-Cu alloy, effectively promotes the electrochemical utilization of deposited Co(OH)₂ even at a high loading amount condition. The great electronic and ionic conduction within the nano-structured electrode improves the energy storage performance of Co(OH)₂ as compared to that for a conventional flat Ni substrate. In this work, the Co(OH)₂ mass specific capacitance, evaluated using cyclic voltammetry (CV), only slightly decreases from 2650 to 2470 F g⁻¹ when the potential sweep rate is substantially increased from 5 to 200 mV s⁻¹. The developed Ni(OH)₂/NiOOH (from the nano-porous framework) incorporates with the deposited Co(OH)₂ upon CV cycling; the mixed hydroxide shows a noticeably synergistic capacitance. Furthermore, the dissolution of Co(OH)₂ in KOH electrolyte is greatly suppressed due to the incorporation of Ni(OH)₂/NiOOH, consequently prolonging the electrode cycle life.     

Understanding RuO2·xH2O/carbon nanofibre composites as supercapacitor electrodes

Composites made from RuO₂·xH₂O particles supported on carbon nanofibres (CNF) have been prepared for supercapacitor electrodes. CNF, produced by Grupo Antolin Ing. SA. using a floating catalyst procedure was treated either in HCl or in HNO₃. Then the composites were obtained by impregnation of CNF with an aqueous RuCl₃·0.5H₂O solution followed by filtering and alkali solution treatment. Heat treatment at 150 °C for 2 h was done. Specific capacitance of the composites has been measured and discussed on the basis of their RuO₂·xH₂O content and RuO₂·xH₂O particle size. The composites having RuO₂·xH₂O contents below 11 wt% show RuO₂·xH₂O particles, which grow from 2 to 4 nm as the RuO₂·xH₂O content increases. The specific capacitance of supported RuO₂·xH₂O, which can be very high (up to 840 F g⁻¹), decreases as the RuO₂·xH₂O content increases and RuO₂·xH₂O particles grow. The composites having RuO₂·xH₂O contents above 11 wt% show RuO₂·xH₂O particles of nearly constant size (4 nm); the effect of increasing the RuO₂·xH₂O content is to increase the amount of particles but not the size of the particles. In these composites the specific capacitance of supported RuO₂·xH₂O is nearly constant (440 F g⁻¹) and close to bare RuO₂·xH₂O (460 F g⁻¹).     

Electrochemical properties of graphene nanosheets/polyaniline nanofibers composites as electrode for supercapacitors

Graphene nanosheets/polyaniline nanofibers (GNS/PANI) composites are synthesized via in situ polymerization of aniline monomer in HClO₄ solution. The PANI nanofibers homogeneously coating on the surface of GNS greatly improve the charge transfer reaction. The GNS/PANI composites exhibit better electrochemical performances than the pure individual components. A remarkable specific capacitance of 1130 F g⁻¹ (based on GNS/PANI composites) is obtained at a scan rate of 5 mV s⁻¹ in 1 M H₂SO₄ solution compared to 402 F g⁻¹ for pure PANI and 270 F g⁻¹ for GNS. The excellent performance is not only due to the GNS which can provide good electrical conductivity and high specific surface area, but also associate with a good redox activity of ordered PANI nanofibers. Moreover, the GNS/PANI composites present excellent long cycle life with 87% specific capacitance retained after 1000 charge/discharge processes. The resulting composites are promising electrode materials for high-performance electrical energy storage devices.     

Preparation and enhanced capacitance of core–shell polypyrrole/polyaniline composite electrode for supercapacitors

Polypyrrole (PPy) nanotubes were synthesized by using the complex of methyl orange (MO)/FeCl₃ as a template. Then the core–shell polypyrrole/polyaniline (PPy/PANI) composite was prepared by in situ chemical oxidation polymerization of aniline on the surface of PPy nanotubes. The morphology and molecular structure were characterized by transmission electron microscopy (TEM), infrared spectroscopy (IR) and X-ray diffraction (XRD). TEM images confirmed that the composite was core–shell nanotubes. The electrochemical properties of the PPy/PANI composite electrode were investigated by cyclic voltammetry (CV), galvanostatic charge–discharge and electrochemical impedance spectroscopy (EIS). The electrochemical experiments showed that the specific capacitance of the PPy/PANI composite was 416 F g⁻¹ in 1 M H₂SO₄ electrolyte and 291 F g⁻¹ in 1 M KCl electrolyte. Furthermore, the composite electrode exhibited a good rate capability and maintained 91% of initial capacity at a current density of 15 mA cm⁻² in 1 M H₂SO₄ electrolyte.     

Electrochemically activated carbon micro-electrode arrays for electrochemical micro-capacitors

Interdigitated carbon micro-electrode arrays for micro-capacitors are fabricated through the carbon microelectromechanical systems (C-MEMS) technique which is based on the carbonization of patterned photoresist. To improve the capacitive behavior, electrochemical activation is performed on carbon micro-electrode arrays. Cyclic voltammetry (CV) and galvanostatic charge-discharge results demonstrate that the electrochemical activation effectively increases the capacitance of the micro-electrode arrays by three orders of magnitude. Although the charge-discharge experiments show the non-ideal behavior of micro-capacitors, the specific geometric capacitance reaches as high as 75 mF cm⁻² at a scan rate of 5 mV s⁻¹ after electrochemical activation for 30 min. The capacitance loss is less than 13% after 1000 CV cycles. These results indicate that electrochemically activated C-MEMS micro-electrode arrays are promising candidates for on-chip electrochemical micro-capacitor application.