Enhanced rate capability of nanostructured three-dimensional graphene/Ni3S2 composite for supercapacitor electrode

Three-dimensional graphene/Ni₃S₂ (3DG/Ni₃S₂) composite electrodes were produced by a facile two-step synthesis route involving chemical vapor deposition (CVD) growth of graphene foam and in situ hydrothermal synthesis of Ni₃S₂. The porous structure of the prepared 3DG is ideal for use as a scaffold for fabricating monolithic composite electrodes. The relative content of Ni₃S₂ initially increased and then decreased with increasing hydrothermal reaction time. The basal surface of the electrode was completely covered after 6 h of hydrothermal reaction. The size of the Ni₃S₂ microspheres also increased with increasing hydrothermal reaction time. The composite electrodes exhibited good specific capacitance (11.529 F cm⁻² at 2 mA cm⁻², i.e., 2611.9 F g⁻¹ at 5 mV s⁻¹) and cyclability (retention of 88.97% capacitance after 1000 charge/discharge cycles at 20 mA cm⁻²). These results are attributed to the fact that the uniform distribution of the Ni₃S₂ microspheres increased the specific surface area of the electrode and facilitated electron transfer and ion diffusion. The 3D multiplexed and highly conductive pathways provided by the defect-free graphene foam also ensured rapid charge transfer and conduction to improve the rate capability of the supercapacitors.     

Polyaniline/MnO2 composite with high performance as supercapacitor electrode via pulse electrodeposition

A method of pulse electrodeposition was proposed to synthesize polyaniline (PANI)/MnO₂ composite in aniline, H₂SO₄, and MnSO₄ aqueous solution. The PANI/MnO₂ composite has rod‐like structure and MnO₂ particles are distributed on PANI uniformly. To evaluate the performance of the as‐prepared materials as supercapacitor electrodes, cyclic voltammetry, galvanostatic charge–discharge measurements, and electrochemical impedance spectroscopy were performed. The PANI/MnO₂ composite shows a higher specific capacitance (810 F g⁻¹) than pure PANI (662 F g⁻¹) at a current density of 0.5 A g⁻¹. The cycle life of the composite was also excellent. After 1,000 cycles, it maintained 86.3% of its initial capacitance. POLYM. COMPOS., 36:113–120, 2015. © 2014 Society of Plastics Engineers     

Ti3C2Tx-foam as free-standing electrode for supercapacitor with improved electrochemical performance

To prevent restacking of the Ti₃C₂T_x layers, the Ti₃C₂T_x-foam has been successfully synthesized through thermal treatment of Ti₃C₂T_x-film with the hydrazine monohydrate. The interconnected porous structure of Ti₃C₂T_x-foam could effectively reduce the restacking of the Ti₃C₂T_x sheets and shorten the diffusion path of ions and accelerate the intercalation/de-intercalation of ions. The Ti₃C₂T_x-foam-80 used as free-standing electrode achieves a high areal capacitance of 271.2 mF/cm² (122.7?F/g) at a scan rate of 5?mV/s in 1?M KOH electrolyte. It also exhibited a high capability rate of 65.5% from 5?mV/s to 100?mV/s and good cycle life with 88.7% retention of its initial after 10,000 cycles at a scan rate of 50?mV/s.     

A high-performance supercapacitor electrode based on freestanding N-doped Ti3C2Tx film

Two-dimensional transition metal carbide (MXene) is a promising electrode material for supercapacitors because of its excellent electrochemical properties. Here, we report a controllable and facile strategy to prepare a freestanding and flexible N-doped Ti₃C₂T_x (N–Ti₃C₂T_x) film electrode with a hydrothermal method using hydrazine hydrate (N₂H₄∙H₂O) as a nitrogen source. At a scan rate of 2 mV s⁻¹, the N–Ti₃C₂T_x film electrode exhibits a high specific capacitance of 340 F g⁻¹ and no capacitance degradation after 10,000 cycles in 1 M H₂SO₄ electrolyte. These results show that the N–Ti₃C₂T_x film could be used as an outstanding electrode material for high-performance supercapacitors. The operation of hydrazine treatment provides a more practical and convenient experimental method for N-doping.     

Preparation and electrochemical performance of modified Ti3C2Tx/polypyrrole composites

MXenes with a large surface area have been widely studied to improve the pseudocapacitance of electrode materials by combining conductive polymer materials. In this article, a superficial strategy to enhance the electrochemical properties by in situ polymerization of a pyrrole monomer between the Ti₃C₂T_x layers modified with 1,5-naphthalene disulfonic acid (NA) and cetyltrimethylammonium bromide (CTAB) was investigated. It is found that polypyrrole (PPy) and Ti₃C₂T_x can be combined through strong interactions between each other, and the specific capacitance of the modified Ti₃C₂T_x/PPy composite was increased to a maximum value of 437 F g⁻¹, which was more than thrice higher than that of pure PPy. The composite also exhibited good cycling performance (76% capacitance retention after 1000 cycles). Moreover, owing to the synergistic effect between the PPy and Ti₃C₂T_x layers, the composite provided better electron or ion transfer and surface redox processes than that of pure PPy, which indicated that this composite can be used as a promising electrode material for supercapacitors. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47003.     

Fabrication of a fibrous MnO2@MXene/CNT electrode for high-performance flexible supercapacitor

As shining stars of 2-dimensional materials, transition metal carbides (MXene) and transition metal oxides have attracted much interest in various energy fields due to their excellent conductive and electrochemical properties. However, big challenge still remains in the accessibility of high-performance fibrous electrodes for flexible supercapacitors. In this paper, MnO₂ nanorods are loaded on MXene sheets to obtain MnO₂@MXene composites by a facile hydrothermal method, which are subsequently coated on carbon nanotube fibers (CNTFs). With a fine control on morphology, the resulting MnO₂@MXene/CNTF electrode exhibits a high specific capacitance of 181.8 F/g at 1 A/g, a capacitance retention of 91% after 5000 charge-discharge cycles, as well as superb flexibility, i.e., neglected capacitance loss at a bending angle of 180°. The as-fabricated flexible composite fiber opens a new door for transition metal carbides and transition metal oxides with great potential in flexible electronics.     

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.     

Enhanced performance by polyaniline/tailored carbon nanotubes composite as supercapacitor electrode material

Polyaniline/tailored carbon nanotubes composite (PANI/TCN) synthesized via situ polymerization of aniline monomer in the presence of tailored carbon nanotubes (TCN) is reported as electrode material for supercapacitors. The morphology, structure, and thermostability of the composite were characterized by scanning electron microscope, Fourier transform infrared, and thermogravimetric analysis. The electrochemical property of the resulting material was systematically studied using cyclic voltammetry and galvanostatic charge–discharge. The results show that the short rod‐like PANI dispersed well in the TCN with three‐dimensional network structure. The as‐prepared composite shows high specific capacitance and good cycling stability. A specific capacitance of 373.5 F g^?1 at a current density of 0.5 A g^?1 was achieved, which is much higher than that of pure PANI (324 F g^?1). Meanwhile, the composite retains 61.7% capacity after 1000 cycles at a scan rate of 50 mV s^?1. The enhanced specific capacitance and capacity retention indicates the potential of composite as a promising supercapacitor electrode material. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 39971.     

Highly stable mesoporous CeO2/CeS2 nanocomposite as electrode material with improved supercapacitor electrochemical performance

The performance of a pseudocapacitor electrode relies largely on the conductivity, cyclic stability, specific surface area and the mesoporosity of the nanomaterials. The CeO₂ is highly stable oxide but poor conductor, on the other hand, CeS₂ is highly conductive but its stability is questionable. Herein, we report the synthesis of CeO₂/CeS₂ nanocomposite, and exploit the properties of both the constituent materials and demonstrates that CeO₂/CeS₂ nanocomposite electrode exhibits an improved capacitance and energy density than CeO₂ nanomaterial. It encompasses large number of pores with a mean size of ～17?nm. The mesoporous nature of the CeO₂/CeS₂ nanocomposite electrode increases its activity, rapid diffusion and transportation of ions and facilitates surface-dependent reversible redox reactions. The nanocomposite electrode demonstrates high stability and its specific capacitance increases almost linearly up to 1000 cyclic voltammetry (CV) cycles. At a current density of 1?A/g it achieves a specific capacitance of 420?F/g. These findings evidently suggest the practical use of CeO₂/CeS₂ nanocomposite as electrode material for future supercapacitors.     

Synthesis of graphene/vitamin C template-controlled polyaniline nanotubes composite for high performance supercapacitor electrode

A graphene nanosheet/polyaniline nanotube (GPNT) composite is prepared for the first time by in-situ chemical oxidative polymerization of aniline using vitamin C as a structure directing agent. The vitamin C molecules lead to the synthesis of polyaniline (PANI) nanotubes through the development of rod-like assembly by H-bonding in an aqueous medium. The initially synthesized graphene oxide/polyaniline nanotubes composite is reduced to graphene using hydrazine monohydrate followed by re-oxidation and protonation of the PANI to produce the GPNT nanocomposite. This novel composite showed a high specific capacitance of 534.37 F/g and an excellent energy density of 74.27 Wh/kg at a constant current of 0.5 mA. Besides, the GPNT composite exhibited excellent cycle life with 91.4% specific capacitance retained after 500 charge-discharge cycles. The excellent performance is due to the synergistic combination of graphene which provides good electrical conductivity and mechanical stability, and PANI nanofiber which deals with good redox activity.     

Fabrication of a sulfonated aramid‐graphene nanoplatelet composite paper and its performance as a supercapacitor electrode

Sulfonated aramid (SA) fiber modified graphene nanoplatelet (GnP) paper was fabricated employing simple vacuum filtration technique. The SA macromolecules were noncovalently attached on the surface of GnP through π?π interactions. Robustness of the film was characterized via dynamic mechanical analysis study. X‐ray photoelectron spectroscopy was employed to investigate the extent of surface functionalization. The specific capacitance of 166 F/g was obtained for the sulfonated graphene nanoplatelet composite paper with 97% of specific capacitance retained after 1000 cycles establishing the cyclic stability of the said composite paper. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45099.     

Self-assembled flower-like FeS2/graphene aerogel composite with enhanced electrochemical properties

Graphene aerogel (GA) supported flower-like ferrous disulfide (FeS₂) composite was synthesis by a two-step self-assembly method using eco-friendly and low-cost precursors. The formation of well-crystallized pyrite FeS₂ and the reduction of graphene oxide (GO) was demonstrated by X-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy. According to the scanning electron microscopy images, the flower-like FeS₂ distributes uniformly on the inter-linking GA networks. The electrochemical tests indicate that the as-prepared GA-FeS₂ exhibits enhanced specific capacitance (313.6 F/g at the current density of 0.5 A/g), which is almost twice as high as that of bare FeS₂ (163.5 F/g). It is noticed that this composite also has excellent cyclability (88.2% retention after 2000 cycles at 10 A/g) and low transfer resistance. A symmetric supercapacitor device with wide potential range was assembled using GA-FeS₂, while its energy density could reach 22.86 Wh/kg. The excellent specific capacitance, good rate capability, and high energy density make it a promising candidate for next generation supercapacitors.     

A simple and efficient method for the preparation of SiO2/PI/AF aerogel composite fabrics and their thermal insulation performance

As a new type of insulation material, aerogels are characterized by a high specific surface area, high porosity, low density and low thermal conductivity, which makes them a new alternative to the use of traditional insulation materials. In this paper, a simple method for preparing aerogel insulation materials is proposed. Specifically, SiO₂/PI/AF (aramid fiber) aerogel composite fabrics were successfully obtained by combining coating technology and finishing processes to use tetraethoxysilane (TEOS) as the precursor, polyimide (PI) powder as the reinforcing agent, and nonwoven AF as the substrate. These composite fabrics were characterized using field-emission scanning electron microscopy (FESEM), tensile testing with an Instron 5967, Fourier transform infrared spectroscopy (FT-IR) and thermal infrared imaging. The results show that the composite fabrics exhibited excellent performance and could effectively block heat transfer. Moreover, the thermal conductivity of the front decreased from 4.08 to 3.91 (W/cm·°C) × 10^-4. This work provides a novel method for the structural design of thermal insulation clothing.     

Cobalt oxide nanocubes as electrode material for the performance evaluation of electrochemical supercapacitor

Porous cobalt oxide (Co₃O₄) nanocubes (NCs) were synthesized by a simple and cost-effective hydrothermal technique for the potential application of electrochemical supercapacitors. The hydrothermally synthesized materials exhibited the small cube like morphology with the average size of ~ 50 to 60 nm. The surface analysis revealed a good surface area, and high pore volume of the synthesized porous Co₃O₄ NCs. The capacitive properties of porous Co₃O₄ NCs electrode were investigated by cyclic voltammetry (CV) in 6 M KOH electrolyte and a high specific capacitance of ~ 430.6 F/g at a scan rate of ~ 10 mV s^?1 was observed. The capacity retention of up to ~ 85% after 1000 cycles was shown by the fabricated porous Co₃O₄ NCs electrode. The porous Co₃O₄ NCs showed excellent structural stability through cycling with promising capacity retention which suggested a good quality of porous Co₃O₄ NCs as electrochemical supercapacitor electrode.     

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.     

Ni@NiCo2O4 core/shells composite as electrode material for supercapacitor

A novel Ni@NiCo₂O₄ core/shells structure consisting of the Ni microspheres skeletons and nanosheet-like NiCo₂O₄ skins was designed and investigated as the electrochemical electrode for supercapacitor. Due to the unique architecture with Ni microspheres as the highly conductive cores improving the electrical conductivity of electrode and external nanosheet-like NiCo₂O₄ shells as the efficient electrochemical active materials facilitating the contact between the electrode and electrolyte, the as-prepared Ni@NiCo₂O₄ exhibited excellent electrochemical performance with high specific capacity of 597 F g⁻¹ (1 A g⁻¹) as well as remarkable capacitance retention of 96% (3000 cycles). These impressive results pave the way to design high-performance electrode materials for energy storage.     

Delafossite CuCrO2 nanoparticles as possible electrode material for electrochemical supercapacitor

Delafossites are popularly known materials for thermoelectric and electrochemical device applications due to their layered structural features. In this paper, delafossite CuCrO₂ nanoparticles (NPs) have been synthesized using a simple chemical procedure and are investigated as a supercapacitor material. To determine the phases of delafossite CuCrO₂ NPs, the morphological and phase formation experiments were conducted using diffraction patterns and microscopic analysis. The cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) studies were performed to evaluate the supercapacitative behavior of delafossite CuCrO₂ NPs. As prepared delafossite CuCrO₂ NPs based electrode showed an outstanding electrochemical property as compared to annealed delafossite CuCrO₂ NPs at 300–500 °C. A good specific capacitance of ～464.7 Fg^-1 at 0.01 Vs^-1 was found for the fabricated supercapacitor using non-annealed delafossite CuCrO₂ NPs based electrode, which was further validated by GCD results. The electrochemical supercapacitor fabricated with both non-annealed and annealed delafossite CuCrO₂ NPs displayed considerably the outstanding cycling stability by maintaining up to ～88% after 5000 cycles. This work sets the pace for a new and efficient method of preparing delafossite CuCrO₂ for high-performance electrochemical supercapacitors.     

Fabrication and electrochemical evaluation of polyhedral PANI-coated Co3O4 electrode for supercapacitor application

In this work, conducting polymer modification on metal oxide surfaces was targeted to improve the composite conductivity and stability for electrochemical energy storage applications. Polyhedral cobalt oxide (Co₃O₄) was prepared using a molten salt combustion method and coated with polyaniline (PANI). The composite (PANI-CoM) was characterized using XRD, TGA, FTIR, FESEM, TEM, and BET. From cyclic voltammetry analysis in 6 M KOH, PANI-CoM shows a high C_S (985 F/g) compared to bare Co₃O₄ (278 F/g), indicating that PANI coating has improved pseudocapacitive charge storability of the electrode. The electrolyte diffusion on the internal active surfaces has increased from 11% to 31%, contributed by the reduction of internal resistance by 29%. Activated carbon and ordered mesoporous carbon (OMC) were used to manufacture two sets of asymmetrical supercapacitor devices, and PANI-CoM/OMC functioned the best performance with an E_D of 22 Wh/kg at a P_D of 400 W/kg.     

石墨烯/聚吡咯复合电极材料超电容性能研究进展

分析了目前石墨烯和聚吡咯(PPy)用作电极材料的不足,详细介绍了近年来超级电容器用石墨烯/PPy复合电极材料的研究进展,指出石墨烯/PPy复合材料在能量转换和存储领域的未来发展方向.     

High performance MnO2 nanoflower supercapacitor electrode by electrochemical recycling of spent batteries

MnO₂ nanoflower is prepared by electrochemical conversion of Mn₃O₄ obtained by heat treatment of spent zinc‒carbon batteries cathode powder. The heat treated and converted powders were characterized by TGA, XRD, FTIR, FESEM and TEM techniques. XRD analyses show formation of Mn₃O₄ and MnO₂ phases for the heat treated and converted powders, respectively. FESEM images indicate the formation of porous nanoflower structure of MnO_2, while, condensed aggregated particles are obtained for Mn₃O₄. The energy band gap of MnO₂ is obtained from UV‒Vis spectra to be 2.4 eV. The electrochemical properties are investigated using cyclic voltammetry, galvanostatic charge‒discharge and electrochemical impedance techniques using three-electrode system. The specific capacitance of MnO₂ nanoflower (309 F g⁻¹ at 0.1 A g⁻¹) is around six times higher than those obtained from the heat treated one (54 F g⁻¹ at 0.1 A g⁻¹). Moreover, it has high capacitance retention up to 93% over 1650 cycles. Impedance spectra of MnO₂ nanoflower show very small resistances and high electrochemical active surface area (340 m² g⁻¹). The present work demonstrates a novel electrochemical approach to recycle spent zinc-carbon batteries into high value supercapacitor electrode.