Fast and reversible surface redox reaction of graphene-MnO2 composites as supercapacitor electrodes

We present a quick and easy method to synthesize graphene-MnO₂ composites through the self-limiting deposition of nanoscale MnO₂ on the surface of graphene under microwave irradiation. These nanostructured graphene-MnO₂ hybrid materials are used for investigation of electrochemical behaviors. Graphene-MnO₂ composite (78 wt.% MnO₂) displays the specific capacitance as high as 310 F g⁻¹ at 2 mV s⁻¹ (even 228 F g⁻¹ at 500 mV s⁻¹), which is almost three times higher than that of pure graphene (104 F g⁻¹) and birnessite-type MnO₂ (103 F g⁻¹). Interestingly, the capacitance retention ratio is highly kept over a wide range of scan rates (88% at 100 mV s⁻¹ and 74% at 500 mV s⁻¹). The improved high-rate electrochemical performance may be attributed to the increased electrode conductivity in the presence of graphene network, the increased effective interfacial area between MnO₂ and the electrolyte, as well as the contact area between MnO₂ and graphene.     

Graphene nanosheets as electrode material for electric double-layer capacitors

Graphene nanosheets (GNSs) with narrow mesopore distribution around 4 nm were mass-produced from natural graphite via the oxidation and rapid heating processes. The effects of oxidant addition on the morphology, structure and electrochemical performance of GNSs as electrode materials for electric double-layer capacitor (EDLC) were systematically investigated. The electrochemical properties of EDLC were influenced by the specific surface area, pore characteristics, layer stacking and oxygen-containing functional group contents of electrode materials. Deeper oxidation makes graphite possess both higher specific surface area and more graphene edges, which are favorable for the enhancement of capacitive performance of EDLC. The electrodes with freestanding graphene nanosheets prepared by coating method exhibited good rate capability and reversibility at high scan rates (to 250 mV s⁻¹) in electrochemical performances. GNS electrode with specific surface area of 524 m² g⁻¹ maintained a stable specific capacitance of 150 F g⁻¹ under specific current of 0.1 A g⁻¹ for 500 cycles of charge/discharge.     

Graphene nanosheets-tungsten oxides composite for supercapacitor electrode

Graphene nanosheets-tungsten oxides (tungsten oxide/tungsten oxide hydrate mixture) (GNS-W) composite was successfully synthesized using a facile approach. WO₃/WO₃·H₂O mixtures were deposited on the graphene nanosheets (GNS) to form the GNS-W composite. The GNS-W composite was characterized by X-ray diffraction (XRD), Raman spectrum, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The as-prepared GNS-W composite was directly fabricated into a supercapacitor electrode for potential energy storage application, and electrochemically tested by cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy. The GNS-W composite electrode exhibits a better electrochemical performance than that of the WO₃/WO₃·H₂O mixtures electrode. A high specific capacitance of about 143.6 F g⁻¹ at a current density of 0.1 A g⁻¹ for the GNS-W composite delivers significant improvement than that for the WO₃/WO₃·H₂O mixtures and GNS electrodes. The impedance studies also suggest that the GNS-W composite electrode shows the lower resistance and high conductivity due to the good interaction between the graphene nanosheets and the WO₃/WO₃·H₂O mixtures. The good electrochemical performance for the GNS-W composite may be attributed to the interaction between the WO₃/WO₃·H₂O mixtures and the edges of graphene nanosheets, which increases the ion diffusion rate as well as the conductivity.     

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.     

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.     

Preparation of functionalized graphene sheets by a low-temperature thermal exfoliation approach and their electrochemical supercapacitive behaviors

Two kinds of functionalized graphene sheets were produced by thermal exfoliation of graphite oxide. The first kind of functionalized graphene sheets was obtained by thermal exfoliation of graphite oxide at low temperature in air. The second kind was prepared by carbonization of the first kind of functionalized graphene sheets at higher temperature in N₂. Scanning electron microscopy images show that both two kinds of samples possess nanoporous structures. The results of N₂ adsorption-desorption analysis indicate that both of two kinds of samples have high BET surface areas. Moreover, the second kind of functionalized graphene sheets has a relatively higher BET surface area. The results of electrochemical tests is as follows: the specific capacitance values of the first kind of functionalized graphene sheets in aqueous KOH electrolyte are about 230 F g⁻¹; the specific capacitance values of the second kind of functionalized graphene sheets with higher BET surface areas are only about 100 F g⁻¹; however, compared with the first kind of functionalized graphene sheets, the second kind has a higher capacitance retention at large current density because of its good conductive behaviors; furthermore, in non-aqueous EC/DEC electrolyte, the specific capacitance values of the first kind sample and the second kind sample are about 73 F g⁻¹ and 36 F g⁻¹, respectively.     

Nano-composite of polypyrrole/modified mesoporous carbon for electrochemical capacitor application

Nano-thin polypyrrole (PPy) layers were coated on chemically modified ordered mesoporous carbon (m-CMK-3) by an in situ chemical polymerization. Structural and morphological characterizations of m-CMK-3/PPy composites were carried out using field emission scanning electron microscopy. Pseudo-capacitive behavior of the deposited PPy layers on m-CMK-3 was investigated by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. As results of this study, the thin layer of PPy in the composite electrode was effective to obtain fully reversible and very fast Faradaic reaction. A maximum discharge capacity of 427 F g⁻¹ or 487 F g⁻¹ after correcting for weight percent of PPy phase at the current density of 5 mA cm⁻², could be achieved in a half-cell setup configuration for the m-CMK-3/PPy composites electrode, suggesting its potential application in electrode material for electrochemical capacitors.     

Preparation and electrochemical capacitance of cobalt oxide (Co3O4) nanotubes as supercapacitor material

Cobalt oxide (Co₃O₄) nanotubes have been successfully synthesized by chemically depositing cobalt hydroxide in anodic aluminum oxide (AAO) templates and thermally annealing at 500 °C. The synthesized nanotubes have been characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrochemical capacitance behavior of the Co₃O₄ nanotubes electrode was investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 6 mol L⁻¹ KOH solution. The electrochemical data demonstrate that the Co₃O₄ nanotubes display good capacitive behavior with a specific capacitance of 574 F g⁻¹ at a current density of 0.1 A g⁻¹ and a good specific capacitance retention of ca. 95% after 1000 continuous charge-discharge cycles, indicating that the Co₃O₄ nanotubes can be promising electroactive materials for supercapacitor.     

Preparation of ordered mesoporous nickel oxide film electrodes via lyotropic liquid crystal templated electrodeposition route

A novel electrochemical route to fabricate ordered mesoporous metal oxide film electrodes has been investigated with particular reference to nickel oxide. Ordered mesoporous nickel oxide films are successfully synthesized by templated electrodeposition of H_I-e nickel hydroxide and followed by heat-treatment in air at various temperatures. The films are characterized physically by thermogravimetry (TG), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The applicability of this film as inexpensive and high-performance supercapacitor electrode material is demonstrated by the electrochemical characterization using cyclic voltammetry (CV) and chronopotentiometry technique. The specific capacitance of the nickel oxide film depends on the annealing temperature, showing a maximum value of 590 F g⁻¹ when the as-deposited film is heat-treated at 250 °C for 1.5 h.     

Factors influencing MnO2/multi-walled carbon nanotubes composite's electrochemical performance as supercapacitor electrode

Poor crystallined α-MnO₂ grown on multi-walled carbon nanotubes (MWCNTs) by reducing KMnO₄ in ethanol are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Brunauer-Emmett-Telle (BET) surface area measurement, which indicate that MWCNTs are wrapped up by poor crystalline MnO₂ and BET areas of the composites maintain the same level of 200 m² g⁻¹ as the content of MWCNTs in the range of 0-30%. The electrochemical performances of the MnO₂/MWCNTs composites as electrode materials for supercapacitor are evaluated by cyclic voltammetry (CV) and galvanostatic charge-discharge measurement in 1 M Na₂SO₄ solution. At a scan rate of 5 mV s⁻¹, rectangular shapes could only be observed for the composites with higher MWCNTs contents. The effect of additional conductive agent KS6 on the electrochemical behavior of the composites is also studied. With a fixed carbon content of 25% (MWCNTs included), MnO₂ with 20% MWCNTs and 5% KS6 has the highest specific capacitance, excellent cyclability and best rate capability, which gives the specific capacitance of 179 F g⁻¹ at a scan rate of 5 mV s⁻¹, and remains 114.6 F g⁻¹ at 100 mV s⁻¹.     

Ru oxide/carbon nanotube composites for supercapacitors prepared by spontaneous reduction of Ru(VI) and Ru(VII)

A novel method based on spontaneous reduction of Ru(VI) and Ru(VII) is reported for the deposition of Ru oxide on multi-walled carbon nanotubes (MWCNT). Both purified and acid functionalized nanotubes (p-MWCNT and a-MWCNT) have been used to produce composite materials for use in high power aqueous supercapacitors. Specific capacitances of 213 ± 16 F g⁻¹ and 184 ± 11 F g⁻¹ were obtained for Ru oxide/p-MWCNT and Ru oxide/a-MWCNT composites, respectively. Specific capacitances for the Ru oxide component were 704 ± 62 F g⁻¹ and 803 ± 72 F g⁻¹, respectively. Current vs. potential curves exhibited capacitance peaks at ca. +0.5 V vs. Ag/AgCl. The Ru oxide/p-MWCNT composite was shown to be stable over 20,000 charge/discharge cycles. An advantage of the method is that no pre-treatment of the MWCNT is required for optimum performance.     

Electrochemical behavior of activated-carbon capacitor material loaded with nickel oxide

In order to enhance specific capacitance and energy density of carbon-based supercapacitor, some nanometer-scale amorphous particles of nickel oxide were loaded into activated-carbon by suspending the activated-carbon in a Ni(NO₃)₂ solution followed by neutralization. A hybrid type electrochemical capacitor was made and tested, in which the activated-carbon loaded with nickel oxide was used as cathode material and activated-carbon was used as anode material. Although the BET surface area of the activated-carbon decreased upon nickel oxide loading compared to that of the starting material, its specific capacitance increased 10.84%, from 175.40 to 194.01 F g⁻¹ and the potential of oxygen evolution on the composite material electrode was 0.076 V higher than that of the pure activated-carbon electrode, in the electrolyte of 6 mol/L KOH solution, so the hybrid capacitor had larger energy density. Similar to the pure activated-carbon electrode, no obvious change appears on the specific capacitances of the composite material electrode at various discharge currents and the composite material electrode exhibiting good power characteristics.     

Investigation of polymer electrolyte hybrid supercapacitor based on manganese oxide-carbon electrodes

A hybrid supercapacitor based on manganese oxide, activated carbon and polymer electrolyte was developed and electrochemically investigated. The capacitive performance obtained from the polymer electrolyte based supercapacitor was similar to that of an aqueous electrolyte based supercapacitor, tested for comparison in the same operative conditions. A durability test carried out for 2500 cycles showed stable and slowly increasing performance. The specific capacitance of hybrid supercapacitor was 48 F g⁻¹ (192 F g⁻¹ as a mean one electrode capacitance), in which that of the positive electrode was 384 F g⁻¹ of MnO₂ and that of negative electrode 117 F g⁻¹ of carbon. The impedance analysis evidenced that although the polymer electrolyte based hybrid supercapacitor showed higher resistance compared to that of the liquid electrolyte based supercapacitor, this drawback was counterbalanced by better ion transport features, which were evident at lower frequencies, where similar values of capacitances were obtained from the different supercapacitors.     

Preparation of a graphene nanosheet/polyaniline composite with high specific capacitance

A graphene nanosheet (GNS)/polyaniline (PANI) composite was synthesized using in situ polymerization. The morphology and microstructure of samples were examined by scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray diffraction (XRD) and Raman spectroscopy. Electrochemical properties were characterized by cyclic voltammetry (CV) and galvanostatic charge/discharge. GNS as a support material could provide more active sites for nucleation of PANI as well as excellent electron transfer path. The GNS was homogeneously coated on both surfaces with PANI nanoparticles (∼2 nm), and a high specific capacitance of 1046 F g⁻¹ (based on GNS/PANI composite) was obtained at a scan rate of 1 mV s⁻¹ compared to 115 F g⁻¹ for pure PANI. In addition, the energy density of GNS/PANI composite could reach 39 W h kg⁻¹ at a power density of 70 kW kg⁻¹.     

Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide

The amorphous nano-structured manganese oxide was electrochemically deposited onto a stainless-steel electrode. The structure and surface morphology of the obtained manganese oxide were studied by means of X-ray diffraction analysis and scanning electron microscopy. The capacitive characteristics of the manganese oxide electrodes were investigated by means of cyclic voltammetry and constant current charge-discharge cycling. The morphological and capacitive characteristics of the hydrous manganese oxide was found to be strongly influenced by the electrochemical deposition conditions. The highest specific capacitance value of ca. 410 F g⁻¹ and the specific power of ca. 54 kW kg⁻¹ were obtained at 400 mV s⁻¹ sweep rate of potentiodynamic deposition condition. The cyclic-life data showed that the specific capacitance was highly stable up to 10,000 cycles examined. This suggests the excellent cyclic stability of the obtained amorphous hydrous manganese oxide for supercapacitor application.     

Physical and electrochemical characterization of CuO-doped activated carbon in ionic liquid

A series of CuO-doped activated carbons (CDACs) were prepared by chemical deposition. The electrochemical behavior of CDACs was investigated in electrochemical capacitors based on ionic liquid 1-ethyl-3-methylimidazolium thiocyanate ([EMIm]SCN) as electrolyte. The results indicated that a diffusion-controlling, reversible redox reaction of CuO particles happened in ionic liquid and porous carbon. When the amount of CuO-doped activated carbon with a specific surface area of 2460 m² g⁻¹ reached 2%, the single electrode average specific capacitance can reach the maximal value of 210 F g⁻¹, about 20% higher than the one used pure activated carbon as electrode material.     

Preparation and electrochemical performance of polyaniline-based carbon nanotubes as electrode material for supercapacitor

Nitrogen-containing carbon nanotubes (CNTs) with open end and low specific surface area were prepared via the carbonization of polyaniline (PANI) nanotubes synthesized by a rapidly mixed reaction. On the basis of analyzing the morphologies and structures of the original and carbonized PANI nanotubes, the electrochemical properties of PANI-based CNTs obtained at different temperatures as electrode materials for supercapacitors using 30 wt.% aqueous solution of KOH as electrolyte were investigated by galvanostatic charge/discharge and cyclic voltammetry. It was found that the carbonized PANI nanotubes at 700 °C exhibit high specific capacitance of 163 F g⁻¹ at a current density of 0.1 A g⁻¹ and excellent rate capability in KOH solution. Using X-ray photoelectron spectroscopy measurement the nitrogen state and content in PANI-CNTs were analysed, which could play important roles for the enhancement of electrochemical performance. When the appropriate content of nitrogen is present, the presence of pyrrole or pyridone and quaternary nitrogen is beneficial for the improvement of electron mobility and the wettability of electrode.     

Mn3O4 nanoparticles embedded into graphene nanosheets: Preparation, characterization, and electrochemical properties for supercapacitors

Mn₃O₄/graphene nanocomposites were synthesized by mixing graphene suspension in ethylene glycol with MnO₂ organosol, followed by subsequent ultrasonication processing and heat treatment. The as-prepared product consists of nanosized Mn₃O₄ particles homogeneously distributed on graphene nanosheets, which has been confirmed by field emission scanning electron microscopy and transmission electron microscopy analysis. Atomic force microscope analysis further identified the distribution of dense Mn₃O₄ nanoparticles on graphene nanosheets. When used as electrode materials in supercapacitors, Mn₃O₄/graphene nanocomposites exhibited a high specific capacitance of 175 F g⁻¹ in 1 M Na₂SO₄ electrolyte and 256 F g⁻¹ in 6 M KOH electrolyte, respectively. The enhanced supercapacitance of Mn₃O₄/graphene nanocomposites could be ascribed to both electrochemical contributions of Mn₃O₄ nanoparticles, functional groups attached to graphene nanosheets, and significantly increased specific surface area.     

Polypyrrole/carbon composite electrode for high-power electrochemical capacitors

Nano-thin polypyrrole (PPy) layers with thickness from ∼5 nm to several 10s nm were deposited on vapor grown carbon fibers (VGCF) by an in situ chemical polymerization. Using different concentrations of the pyrrole could control the thicknesses of deposited PPy layers. Surface morphology and thickness of the deposited PPy layers were confirmed by means of scanning electron microscopy and scanning transmission emission microscopy. Pseudo-capacitive behavior of the deposited PPy layers on VGCF investigated by means of cyclic voltammetry. Then, the PPy/VGCF composites were mixed with activated carbons (AC) at various mixing ratios. For the PPy/VGCF/AC composite electrodes, characteristics of specific capacitance and power capability were examined by half-cell tests. As results of this study, it was investigated that nano-thin PPy layer below ∼10 nm deposited on VGCF had high pseudo-capacitance and fast reversibility. Its specific capacitance per averaged weight of active material (PPy) was obtained as ∼588 F g⁻¹ at 30 mV s⁻¹ and maintained as ∼550 F g⁻¹ at 200 mV s⁻¹ of scan rate. Also, from the mixing 60 wt.% of the PPy/VGCF with 25 wt.% of AC, the PPy/VGCF/AC composite electrode exhibited higher power capability maintaining the specific capacitance per active materials of PPy and AC as ∼300 F g⁻¹ at 200 mV s⁻¹ in 6 M KOH.     

Reduced chemically modified graphene oxide for supercapacitor electrode

An efficient active material for supercapacitor electrodes is prepared by reacting potassium hydroxide (KOH) with graphene oxide followed by chemical reduction with hydrazine. The electrochemical performance of KOH treated graphene oxide reduced for 24 h (reduced chemically modified graphene oxide, RCMGO-24) exhibits a specific capacitance of 253 F g^-1 at 0.2 A g^-1 in 2 M H₂SO₄ compared to a value of 141 F g^-1 for graphene oxide reduced for 24 h (RGO-24), and good cyclic stability up to 3,000 cycles. Interestingly, RCMGO-24 demonstrated a higher specific capacitance and excellent cycle stability due to its residual oxygen functional groups that accelerate the faradaic reactions and aid in faster wetting. This non-annealed strategy offers the potential for simple and cost-effective preparation of an active material for a supercapacitor electrode.