NiO-based composite electrode with RuO2 for electrochemical capacitors

NiO/RuO₂ composite materials were prepared for use in electrochemical capacitors (ECs) by co-precipitation method followed by heat treatment. X-ray diffraction (XRD) spectra indicated that no new structural materials were formed and ruthenium oxide particles were coated by NiO particles. RuO₂ partly introduced into NiO-based electrode had improved its electrochemical performance and capacitive properties by using electrochemical measurements. A maximum specific capacitance of 210 F/g was obtained for NiO-based composite electrode with 10 wt.% RuO₂ in the voltage range from −0.4 to 0.5 V in 1 mol/l KOH solution. By comparison of effect of modified modes on the specific capacitance, chemically modified composite electrodes had more stable cycling properties than those of physically modified electrodes. After 200 cycles, specific capacitance of NiO-based chemical composite electrode with 5 wt.% RuO₂ kept 95% above, while that of physical electrode was only 79% of initial specific capacitance.     

Disordered carbon negative electrode for electrochemical capacitors and high-rate batteries

In order to understand the properties of high-rate capability and cycleability for a disordered carbon negative electrode in LiPF₆/PC based electrolyte solution, the cell performance tests with various rates and depth of discharges (DODs) has been studied by spectroscopic and electrochemical analyses. From the charge-discharge measurements, a surface carbon-edge redox reaction occurring between a carbonyl (C_edgeO) and a lithium alkoxide (C_edge-OLi) that delivers a large capacity was found fast and high cycleability at only shallow DOD (2.0-0.4 V). The limited or shallow charge-discharge cycling utilizing such facile and reversible action of the C_edgeO/C_edge-OLi of the disordered carbon is suited to an application for an negative electrode of asymmetric hybrid capacitors. A deep DOD discharge (2.0-0.0 V) revealed the existence of some complex processes involving a lithium cluster deposition at pores or microvoids as well as a lithium ion intercalation at graphene layers. The cluster deposition at pores was found to be relatively fast and reproducible. The lithium ion intercalation at graphenes and the subsequent cluster deposition at microvoids were found to be slow and degrade the cycleability after 100 cycles because of the accumulation of a thick and low-ion-conductive solid electrolyte interface (SEI) film on surface.     

Performance evaluation of CNT/polypyrrole/MnO2 composite electrodes for electrochemical capacitors

A ternary composite of CNT/polypyrrole/hydrous MnO₂ is prepared by in situ chemical method and its electrochemical performance is evaluated by using cyclic voltammetry (CV), impedance measurement and constant-current charge/discharge cycling techniques. For comparative purpose, binary composites such as CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ are prepared and also investigated for their physical and electrochemical performances. The specific capacitance (SC) values of the ternary composite, CNT/hydrous MnO₂ and polypyrrole/hydrous MnO₂ binary composites estimated by CV technique in 1.0 M Na₂SO₄ electrolyte are 281, 150 and 35 F g⁻¹ at 20 mV s⁻¹ and 209, 75 and 7 F g⁻¹ at 200 mV s⁻¹, respectively. The electrochemical stability of ternary composite electrode is investigated by switching the electrode back and forth for 10,000 times between 0.1 and 0.9 V versus Ag/AgCl at 100 mV s⁻¹. The electrode exhibits good cycling stability, retaining up to 88% of its initial charge at 10,000th cycle. A full cell assembled with the ternary composite electrodes shows a SC value of 149 F g⁻¹ at a current loading of 1.0 mA cm⁻² during initial cycling, which decreased drastically to a value of 35 F g⁻¹ at 2000th cycle. Analytical techniques such as scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), Brunauer-Emmet-Teller (BET) surface area measurement and inductively coupled plasma-atomic emission spectrometry (ICP-AES) are also used to characterize the composite materials.     

Morphological reason for enhancement of electrochemical double layer capacitances of various acetylene blacks by electrochemical polarization

Enhancement of electrochemical capacitance and morphological variations of various acetylene blacks caused by electrochemical polarization are presented. Acetylene blacks of different mean particle diameters were modified by air-oxidation and heat treatment to diversify the morphologies of the acetylene blacks before electrochemical polarization. The various acetylene blacks were electrochemically oxidized at 1.6 V (vs. Ag/AgCl) for 10 s and the polarization step was repeated until the capacitance values did not change any longer. These polarization steps enhanced the capacitances of the acetylene blacks and the specific enhancement factors range from 2 to 5.5. Such an enhancement is strongly related to morphological modification as revealed by transmission electron microscopic observations. The electrochemical polarization resulted in formation of tiny graphene sheets on the wide graphitic carbon surfaces, which were most responsible for the observed capacitive enhancement. Although the pseudo-capacitance increased after polarization by forming oxygenated species on the surfaces, its contribution to the total capacitance was less than 10%. The mechanism of the formation of the tiny graphene sheets during the electrochemical oxidation is described schematically.     

High-capacitance carbon electrode prepared by PVDC carbonization for aqueous EDLCs

Porous carbons with high-volumetric capacitance in aqueous electric double layer capacitors (EDLCs) were simply prepared by poly(vinylidene chloride) (PVDC) carbonization at high temperature without activation or any other additional processes. The PVDC-derived carbon is microporous with Brunauer-Emmett-Teller (BET) surface area about 1200 m² g⁻¹. As it possesses not only high-gravimetric capacitance (262 F g⁻¹) but also high-electrode density (0.815 g cm⁻³), the PVDC-derived carbon present an outstanding high-volumetric capacitance of 214 F cm⁻³, twice over of the commercial carbon Maxsorb-3 with a high-surface area of 3200 m² g⁻¹. The PVDC-derived carbon also exhibit good rate performance, indicating that it is a promising electrode material for EDLCs.     

A novel high power symmetric ZnO/carbon aerogel composite electrode for electrochemical supercapacitor

We present, for the first time, a new material of symmetric electrochemical supercapacitor in which zinc oxide (ZnO) with carbon aerogel (CA) was used as active material. Physical properties of ZnO/CA composite were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that ZnO has single hexagonal structure and the grain size increases with increase of ZnO compository. The result of cyclic voltammetry indicates that the specific capacitance of ZnO/CA composite in 6 M KOH electrolyte was approximately 25 F/g at 10 mV/s for 2:1 composition. AC impedance analysis reveals that ZnO with carbon aerogel powder enhanced the conductivity by reducing the internal resistance. Galvanostatic charge/discharge measurements were done at various current densities, namely 25, 50, 75, and 100 mA/cm². It was found that the cells have excellent electrochemical reversibility and capacitive characteristics in KOH electrolyte. The maximum capacitance of the ZnO/CA supercapacitor was 500 F/g at 100 mA/cm². It has been observed that the specific capacitance is constant up to 500 cycles at all current densities, which implies that the dendrite formation was controlled.     

Influence of oxidation level on capacitance of electrochemical capacitors fabricated with carbon nanotube/carbon paper composites

Gaseous oxidation of carbon papers (CPs) decorated with carbon nanotubes (CNTs) with varying degrees of oxidation was conducted to investigate the influence of surface oxides on the performance of electrochemical capacitors fabricated with oxidized CNT/CP composites. The oxidation period was found to significantly enhance the O/C atomic ratio on the composites, and the increase in oxygen content upon oxidation is mainly contributed by the formation of CO and C-O groups. The electrochemical behavior of the capacitors was tested in 1 M H₂SO₄ within a potential of 0 and 1 V vs. Ag/AgCl. Both superhydrophilicity and specific capacitance of the oxidized CNT/CP composites were found to increase upon oxidation treatment. A linearity increase of capacitance with O/C ratio can be attributed to the increase of the population of surface oxides on CNTs, which imparts excess sites for redox reaction (pseudocapacitance) and for the formation of double-layer (double-layer capacitance). The technique of ac impedance combined with equivalent circuit clearly showed that oxidized CNT/CP capacitor imparts not only enhanced capacitance but also a low equivalent series resistance.     

Pressure evolution in propylene carbonate based electrochemical double layer capacitors

Increasing the available cell voltage for electrochemical double layer capacitors (EDLC) is one route to simultaneously increase energy density and power density of the EDLC. Increased cell voltage may, however, introduce faradaic reactions such as ion insertion and electrolyte decomposition, which potentially limit the lifetime of the device. Using a purpose designed pressure cell, we have, for the first time, measured the pressure increase in capacitor cells based on real EDLC electrode coils in 1 M (C₂H₅)₄NBF₄/propylene carbonate electrolyte during cycling between 0 and 2.5 V and for constant cell voltages up to 3 V. During cycling a reversible pressure decrease was observed upon charging. An irreversible pressure increase was monitored during load tests at constant cell voltages above 2.5 V. The absolute amount of gases evolved could be determined by means of simultaneous compressibility monitoring.     

Decrease in equivalent series resistance of electric double-layer capacitor by addition of carbon nanotube into the activated carbon electrode

An electric double layer capacitor (EDLC) was fabricated with the addition of carbon nanotubes (CNTs) to the polarizable electrodes to act as a conducting material. This EDLC showed a low equivalent series resistance of 2.5 Ω. This value was lower than that of an EDLC fabricated with the addition of acetylene black, which is widely used in commercial EDLCs.     

Polypyrrole/MnO2 composites and their enhanced electrochemical capacitance

The composites of polypyrrole (PPY) and MnO₂ have been prepared through chemical oxidation of pyrrole monomer and MnO₂ suspension with ammonium peroxysulfate at low temperature. The morphology and structure of materials were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), Transmission electron microscopy (TEM), thermal gravity analysis ‐ differential thermal gravity (TG‐DTG), and X‐ray diffraction (XRD) measurements. The electrochemical properties of the composite were investigated by galvanostatic charge–discharge and electrochemical impedance spectroscopy. The specific capacitance of the composite electrode is 352.8 F/g at a current of 8 mA/cm² in Na₂SO₄ electrolyte of 0.5 mol/L, which is much higher than that of 246.2 F/g and 103.5 F/g of PPY and MnO₂, respectively. A convenient and effective technique has been developed to fabricate composite materials of PPY and MnO₂ promising for designing new capacitors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.     

Activated carbon fiber cloths as electrodes for high performance electric double layer capacitors

Activated carbon fiber cloth (ACFC) electrodes with high double layer capacitance and good rate capability were prepared from polyacrylonitrile (PAN) fabrics by optimizing the carbonization temperature prior to CO₂ activation. The carbonization temperature has a marked effect on both the pore structure and the electrochemical performances of the ACFCs. Moderate carbonization at 600 °C results in higher specific surface area and larger pore size, and hence higher capacitance and better rate capability. The specific capacitance of the ACFCs in 6 mol L⁻¹ KOH aqueous solution can be as high as 208 F g⁻¹. It remains 129 F g⁻¹ as the current density increases to 10 000 mA g⁻¹.     

Mixed bi-material electrodes based on LiMn2O4 and activated carbon for hybrid electrochemical energy storage devices

The performance of mixed bi-material electrodes composed of the battery material, LiMn₂O₄, and the electrochemical capacitor material, activated carbon, for hybrid electrochemical energy storage devices is investigated by galvanostatic charge/discharge and pulsed discharge experiments. Both, a high and a low conductivity lithium-containing electrolyte are used. The specific charge of the bi-material electrode is the linear combination of the specific charges of LiMn₂O₄ and activated carbon according to the electrode composition at low discharge rates. Thus, the specific charge of the bi-material electrode falls between the specific charge of the activated carbon electrode and the LiMn₂O₄ battery electrode. The bi-material electrodes have better rate capability than the LiMn₂O₄ battery electrode. For high current pulsed applications the bi-material electrodes typically outperform both the battery and the capacitor electrode.     

Studies on Me/Al-layered double hydroxides (Me = Ni and Co) as electrode materials for electrochemical capacitors

Me/Al-layered double hydroxides (Me=Ni and Co) prepared by the chemical co-precipitation method have been shown to be outstanding novel materials for electrochemical capacitors. The crystalline structure and the electrochemical properties of the electrodes have been studied by considering the effect of the mole ratio of nickel/cobalt. X-ray diffraction analysis shows that the materials belong to hexagonal system with layered structure. Cyclic voltammetric measurements indicate that Me/Al-layered double hydroxides with the Ni/Co mole ratio of 4:6 exhibit excellent capacitive properties within the potential range of 0.0-0.6 V versus Hg/HgO in 6 mol/L KOH electrolyte. Charge/discharge behaviors have been observed with the highest specific capacitance values of 960 F/g at the current density of 400 mA/g. Impedance studies show that the enhanced electrical properties and high frequency response are attributed to the presence of Co oxides.     

Polyaniline/multi-walled carbon nanotube composites with core-shell structures as supercapacitor electrode materials

Composites with core-shell structures consisting of polyaniline and carbon nanotubes were prepared via in situ polymerization of aniline monomers by using multi-walled carbon nanotubes with minimized defects as templates. The strong interaction in such conjugated systems greatly improves the charge-transfer reaction between polyaniline and the carbon nanotube. Influences of the thickness of the polyaniline layer on the surface of the carbon nanotubes on the electrochemical properties of the resulting composites are discussed. The highest specific capacitance of 560 F/g was achieved by using a composite with 66 wt% polyaniline content as the supercapacitor electrode. Additionally, enhancement of the capacity retention was observed, with the composite losing only 29.1% of the maximum capacity after 700 cycles, and then remaining stable.     

1-Methyl-3-butylimidazolium tetraflouroborate with activated carbon for electrochemical double layer supercapacitors

This article presents the main features of electrochemical double layer supercapacitors, made of nanostructured carbon materials with specially selected and optimized porosity structure and electrolyte based on solvent-free ionic liquid as follows 1-methyl-3-butylimidazolium tetrafluoroborate (1Me3BuImBF₄). The performance of supercapacitor was carried out by cyclic voltammetry and galvanostatic charge/discharge measurements. The main characteristics of stacked supercapacitors exhibit a nominal voltage 3.0 V and a maximum cell voltage 3.5 V as well as a specific capacitance (individual electrode of supercapacitor) of 111 F/g. The specific energy of 4.1 Wh/kg and specific power of 1.7 W/kg for industrial stacked supercapacitor has been achieved.     

Study on synthesis of low surface area activated carbons using multi-step activation for use in electric double layer capacitor

Low surface area activated carbon derived from compact mesocarbon microbeads (MCMB2010) was synthesized using a lower amount of KOH (1:1 weight ratio of KOH to MCMB) than normally used followed by electrochemical activation. The specific capacitance of the activated carbon heat treated at between 650 and 900 °C was increased up to ca. 118 F/cc (half cell base, 750 °C-heat treated sample) after electrochemical activation, even with a low surface area carbon (<50 m²/g). The morphology of low surface area activated MCMB determined by FE-SEM showed a smooth carbon surface without pores. The charge/discharge profiles were similar to those of conventional activated carbon. The specific capacitance of the activated samples increased with increasing heat treatment up to 850 °C after electrochemical activation. However, it was lower for the sample heat treated at 900 °C.     

Preparation and electrochemistry of NiO/SiNW nanocomposite electrodes for electrochemical capacitors

This paper studies nickel oxide/silicon nanowires (NiO/SiNWs) as composite thin films in electrodes for electrochemical capacitors. The SiNWs as backbones were first prepared by chemical etching, and then the Ni/SiNW composite structure was obtained by electroless plating of nickel onto the surface of the SiNWs. Next, the NiO/SiNW nanocomposites were fabricated by annealing Ni/SiNW composites at different temperatures in an oxygen atmosphere. Once the electrodes were constructed, the electrochemical behavior of these electrodes was investigated with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). In 2 M KOH solution, the electrode material was found to have novel capacitive characteristics. Finally, when the NiO/SiNW composites were annealed at 400 °C, the maximum specific capacitance value was found to be as high as 681 F g⁻¹ (or 183 F cm⁻³), and the probing of the cycling life indicated that only about 3% of the capacity was lost after 1000 charge/discharge cycles. This study demonstrated that NiO/SiNW composites were the optimal electrode choice for electrochemical capacitors.     

Nanostructured V2O5 and its nanohybrid with MXene as an efficient electrode material for electrochemical capacitor applications

Vanadium pentoxide (V₂O₅) is an excellent electrode material for electrochemical capacitor (ECCs) applications, but its lower electrical conductivity is the primary obstacle that restricts its practical applications. This obstacle can be eliminated by forming its nanohybrid (NCs) with a highly capacitive and conductive matrix such as MXene. MXene is a new two-dimensional (2D) material with good electronic conductivity and a larger specific surface area, making it a very suitable substrate for composite formation. Unfortunately, the two-dimensional MXene sheets stacked quickly, limiting their specific surface area and charge/mass transport properties. Here we used the hydrothermal approach to fabricate V₂O₅ nanowires (NWs) and form their nanohybrid with MXene via the ultrasound route. To assess electrochemical suitability, the fabricated samples were loaded onto a carbon cloth (CC) and used as a working electrode in the half-cell configuration. The nanohybrid (V₂O₅/MXene) sample showed a good specific capacity (C_sp) of 768 F/g (at 1 A/g) because of its greater surface area, hybrid composition, excellent electrical conductivity, and passive nanostructure. It also showed superior cyclic, electrochemical and mechanical capability and maintained a specific capacity of 93.3%, even after completion of 6000 GCD tests. In addition, the nanohybrid sample electrode also exhibits superb rate performance and lost only 14.4% of its initial specific capacity on increasing the applied current density from 1 to 5 A/g. There is no doubt that V₂O₅ NWs inter-stack between MXene nanosheets to develop effective interface interaction and suppress their stacking.