Coal tar residues-based nanostructured activated carbon/Fe3O4 composite electrode materials for supercapacitors

Oxygen-rich activated carbon with a three-dimensional network structure was prepared by chemical activation of coal tar residues with potassium hydroxide and subsequent carbonization treatment. Nanostructured Fe₃O₄/AC composites were then prepared by simple chemical coprecipitation method and were used as active electrode materials for supercapacitors. The electrochemical behaviors of Fe₃O₄/AC nanocomposites were characterized by cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy in 1.0 M Na₂SO₃ electrolyte. It was shown that the specific capacitance of Fe₃O₄/AC nanocomposites reached 150 F g^?1 at a current density of 3.0 A g^?1 and was a great improvement over Fe₃O₄ or AC alone. Furthermore, as-prepared Fe₃O₄/AC nanocomposites exhibited long cycle life without obvious capacitance fading even after 1,000 charge/discharge cycles. Compared with pure Fe₃O₄ and AC, the significant enhanced electrochemical performance of Fe₃O₄/AC nanocomposites could be reasonably attributed to the positive synergetic effect between Fe₃O₄ and AC.     

Thiourea aldehyde resin-based carbon/graphene composites for high-performance supercapacitors

Thiourea aldehyde resin-based heteroatom doping carbon and graphene composites (RHDC/GN) were prepared by an in situ polymerization and carbonization. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that thiourea aldehyde resin deposited on lamellar GO flakes during the polymerization and RHDC/GN composites had a hierarchical structure. The specific capacitance of the RHDC/GN composites was high up to 355 F g^?1, much higher than that of the pure thiourea aldehyde resin-based heteroatom doping carbon (RHDC) with specific capacitance of 135 F g^?1 at a current density of 1.0 A g^?1 in 6-M KOH electrolyte. And the hetroatoms in RHDC/GN composites increase the specific capacitance, and GN enhances the conductivity of the electrodes which is beneficial to improving electrochemical cycling stability of the electrode significantly. The specific capacitance retains 90.97% after 5000 charge-discharge processes at 10 A g^?1, which provides potential as supercapacitors.     

Graphene/poly(ortho-phenylenediamine) nanocomposite material for electrochemical supercapacitor

Reduced graphene oxide was synthesized by simple chemical processing of graphite. Electron microscopy investigations of synthesized graphene showed slightly folded transparent sheets with a few square micrometers dimension. Poly(ortho-phenylenediamine)/graphene/Pt electrode was electrochemically fabricated in a 2.0-M H₂SO₄ solution by means of multiple potential cycling. Due to the catalytic effect of graphene on the oxidative electropolymerization of ortho-phenylenediamine, the ortho-phenylenediamine/graphene (PoPD/GR) nanocomposite showed greatly enhanced electrical properties and excellent capacitive behavior. Electrochemical impedance spectroscopy, galvanostatic charge/discharge curves, and voltammetric investigations revealed that PoPD/GR nanocomposite represented good capacitive behavior with a specific capacitance as high as 308.3 F g^?1 at 0.1 A g^?1. It is almost three times higher than that of pure graphene (111.7 F g^?1). In addition, the nanocomposite electrode retained more than 99 % of the initial capacity after 1,500 cycles at a current density of 1 A g^?1.     

In situ synthesis of crosslinked-polyaniline nano-pillar arrays/reduced graphene oxide nanocomposites for supercapacitors

Crosslinked-polyaniline (CPA) nano-pillar arrays adsorbed on the surface of reduced graphene oxide (RGO) sheets were synthesized by in situ solution polymerization through two steps of reduction. The electrochemical analyses demonstrated that the befittingly reduced CPA/RGO composite exhibited high performance as electrode materials for supercapacitors. The CPA/RGO composite showed very high specific capacitance of 1532 F g^?1 at a scan rate of 10 mV s^?1 or 694 F g^?1 at a current density of 2 A g^?1 in 1 M H₂SO₄ electrolyte, as well as great energy density of 61.4 W h kg^?1 at a current density of 2 A g^?1. The electrode material also had decent power density of 4 kW kg^?1 at a current density of 10 A g^?1, and good cycling stability of 92.5 % capacitance retained after 500 cycles of cyclic voltammetry at 500 mV s^?1. The neat microstructures and super electrochemical properties suggest the potential use of the composites in supercapacitors.     

MWCNTs/metal (Ni, Co, Fe) oxide nanocomposite as potential material for supercapacitors application in acidic and neutral media

Supercapacitive properties of synthesised metal oxides nanoparticles (MO where M = Ni, Co, Fe) integrated with multi-wall carbon nanotubes (MWCNT) on basal plane pyrolytic graphite electrode (BPPGE) were investigated. Successful modification of the electrode with the MWCNT-MO nanocomposite was confirmed with spectroscopic and microscopic techniques. Supercapacitive properties of the modified electrodes in sulphuric acid (H₂SO₄) and sodium sulphate (Na₂SO₄) electrolytes were investigated using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic constant current charge–discharge (CD) techniques. The specific capacitance values followed similar trend with that of the cyclic voltammetry and the electrochemical impedance experiments and are slightly lower than values obtained using the galvanostatic charge–discharge cycling. MWCNT-NiO-based electrode gave best specific capacitance of 433.8 mF?cm^?2 (ca 2,119 F?g^?1) in H₂SO₄. The electrode exhibited high electrochemical reproducibility with no significant changes over 1,000 cyclic voltammetry cycles.     

Electrospun porous MnMoO<Subscript>4</Subscript> nanotubes as high-performance electrodes for asymmetric supercapacitors

MnMoO₄ nanotubes of diameter about 120 nm were successfully synthesized by a single-spinneret electrospinning technique followed by calcination in air, and their structural, morphological, and electrochemical properties were studied with the aim to fabricate high-performance supercapacitor devices. The obtained MnMoO₄ nanotubes display a 1D architecture with a porous structure and hollow interiors. Benefiting from intriguing structural features, the unique MnMoO₄ nanotube electrodes exhibit a high specific capacitance, excellent rate capability, and cycling stability. As an example, the tube-like MnMoO₄ delivers a specific capacitance of 620 F g^?1 at a current density of 1 A g^?1, and 460 F g^?1 even at a very high current density of 60 A g^?1. Remarkably, almost no decay in specific capacitance is found after continuous charge/discharge cycling for 10,000 cycles at 1 A g^?1. An asymmetric supercapacitor fabricated from this MnMoO₄ nanotubes and activated carbon displayed a maximum high energy density of 31.7 Wh kg^?1 and a power density of 797 W kg^?1, demonstrating a good prospect for practical applications in energy storage electronics.     

Fabrication of novel solid-state supercapacitor using a Nafion polymer membrane with graphene oxide/multiwalled carbon nanotube/polyaniline

In the current work, the effect of aniline concentration on the polymerization process and supercapacitive behavior of graphene oxide/multiwalled carbon nanotubes/polyaniline (GMP) nanocomposites were studied. Based on the obtained results, GMP nanocomposite with 0.5 M aniline (GMP5) was selected as the optimum concentration in terms of high current density and high specific capacitance. Nafion-based ionic polymer-free metal composite (IPFMC) supercapacitor was fabricated for the GMP5 nanocomposite. Solid-state symmetric supercapacitor was made after spraying of GMP5 in. on both sides of Nafion membrane. The electrochemical properties were investigated by cyclic voltammetry (CV), galvanostatic charge–discharge (CD), and electrochemical impedance spectroscopy (EIS) techniques in 0.5 M Na₂SO₄.The specific capacitance of 383.25 F g^?1 (326 mF cm^?2) and 527.5 F g^?1 (42 mF cm^?2) was obtained for the GMP5 in solid-state supercapacitor and three-electrode cell at a scan rate of 10 mV s^?1, respectively. The maximum energy and power densities of 53.64 and 1777.4 W kg^?1 were obtained for the IPFMC-based supercapacitor.

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Graphical abstract Schematic of the solid-state supercapacitor based on the GMP5 nanocomposite

     

α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films by liquid phase deposition: low-cost option for supercapacitor

In the present study, iron oxide (α-Fe₂O₃) thin films with good adhesion on stainless steel substrates are deposited by liquid phase deposition (LPD) technique, which is additive and binder-free. Iron oxyhydroxide (FeOOH) thin films are formed by means of a ligand-exchange equilibrium reaction of metal-fluoro complex ions and an F^?ions consuming reaction by using boric acid (H₃BO₃) as a scavenging agent. These films are annealed at 500 °C to get α-Fe₂O₃ thin films. The transformation from hydrophobic to hydrophilic nature of the films is observed due to annealing. The films are characterized by different techniques. The α-Fe₂O₃ film is checked for electrochemical supercapacitive performance in Na₂SO₃ solutions of various concentrations. Specific capacitance is calculated from cyclic voltammetry at numerous scan rates (5–200) mV s^?1. The highest obtained value of specific capacitance is 582 F g^?1 at 5 mV s^?1 for 0.5 M Na₂SO₃ electrolyte. The maximum values of specific power and specific energy are 6.9 and 53.4 Wh kg^?1 from the charge-discharge curve at the current density 2 mA cm^?2 in 0.5 M Na₂SO₃ electrolyte.     

Facile fabrication of mesoporous manganese oxides as advanced electrode materials for supercapacitors

Mesoporous manganese oxides (MnO₂) were synthesized via a facile chemical deposition strategy. Three kinds of basic precipitants including sodium carbonate (Na₂CO₃), sodium bicarbonate (NaHCO₃), and sodium hydroxide (NaOH) were employed to adjust the microstructures and surface morphologies of MnO₂ materials. The obtained MnO₂ materials display different microstructures. Great differences are observed in their specific surface area and porosity properties. The microstructures and surface morphologies characteristics of MnO₂ materials largely determine their pseudocapacitive behavior for supercapacitors. The MnO₂ prepared with Na₂CO₃ precipitant exhibits the optimal microstructures and surface morphologies compared with the other two samples, contributing to their best electrochemical performances for supercapacitors when conducted either in the single electrode tests or in the capacitor measurements. The optimal MnO₂ electrode exhibits a high specific capacitance (173 F g^–1 at 0.25 A g^?1), high-rate capability (123 F g^?1 at 4 A g^?1), and excellent cyclic stability (no capacitance loss after 5,000 cycles at 1 A g^?1). The optimal activated carbon//MnO₂ hybrid capacitor exhibits a wide working voltage (1.8 V), high-power and high-energy densities (1,734 W kg^?1 and 20.9 Wh kg^?1), and excellent cycling behavior (93.8 % capacitance retention after 10,000 cycles at 1 A g^?1), indicating the promising applications of the easily fabricated mesoporous MnO₂ for supercapacitors.     

Electrochemical exfoliation and in situ carboxylic functionalization of graphite in non-fluoro ionic liquid for supercapacitor application

Simultaneous electrochemical generation and functionalization of nano-sized graphite from graphite had been carried out in a non-fluoroanion-based ionic liquid, namely, triethylmethylammonium methylsulfate (TEMAMS) containing water and acetonitrile (AN) in different weight ratios. The oxygen-based functional groups attached with the exfoliated material had been identified using Fourier transform infrared spectroscopy (FTIR), and morphological changes were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). A symmetrical supercapacitor was fabricated using the exfoliated nano-sized graphite, and the influence of surface functionalities on its performance was investigated using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge–discharge cycles (CC). The highest specific capacitance (C _sp) value of 140 F g^?1 at 0.25 A g^?1 was obtained in 1.0 M H₂SO₄, followed by aqueous TEMAMS (125 F g^?1), TEMAMS/acetonitrile (115 F g^?1), and TEMAMS (106 F g^?1) at 0.10 A g^?1.     

KOH direct treatment of kombucha and in situ activation to prepare hierarchical porous carbon for high-performance supercapacitor electrodes

Kombucha, a renewable biomass, has been successfully utilized as an accessible carbon source to fabricate kombucha-derived hierarchical porous carbon (KHPC) by KOH direct treatment and in situ activation. The prepared KHPC shows an interconnected hierarchical porous structure, a pore volume of 0.41 cm³ g^?1, and a specific surface area of 917 m² g^?1. Due to the multiple synergistic effects of these advantages, the KHPC-3 exhibits a high specific capacitance of 326 F g^?1 at a current density of 1 A g^?1 in 6 M KOH, good rate capability of 82% retention from 1 to 20 A g^?1, and cycling performance with 91.3% retention over 5000 cycles. Moreover, the KHPC-3 symmetric supercapacitor reveals a good energy density of 20.97 Wh kg^?1 at a power density of 871.2 W kg^?1 and retains 8.08 Wh kg^?1 at 6330 W kg^?1 in 1 M Na₂SO₄ electrolyte. Therefore, the KHPC obtained via the simple synthesis process shows great promise as an electrode material in energy storage devices.     

Resorcinol-formaldehyde carbon spheres/polyaniline composite with excellent electrochemical performance for supercapacitors

Well-dispersed resorcinol-formaldehyde-based carbon spheres (RFCs) have been prepared by the polycondensation of resorcinol and formaldehyde with ammonia as catalyst and subsequent carbonization of the obtained polymer. In situ polymerization of the aniline occurred in the suspension of the RFC, and RFC was surrounded by the polyaniline (PANI) wires. The PANI and RFC hybrid network (PRFC) formed gradually. In a three-electrode mode, the specific capacitance (C _sp) of PRFC reaches 315 F g^?1 at a current density of 1 A g^?1 in 2 M H₂SO₄, much higher than that of pure PANI (225 F g^?1) and RFC (121.7 F g^?1). Furthermore, the C _sp of PRFC retains 80.0 % after 1000 charge-discharge processes at a current density of 5 Ag^?1. The enhanced electrochemical performance of the PRFC came from its homogeneous three-dimensional hierarchical network structure, good electric conductivity of the PANI around the RFC, and the synergistic effect between the RFC and PANI.     

Synthesis of micro- and mesoporous carbon spheres for supercapacitor electrode

Micro- and mesoporous carbon spheres (MMCSs) are synthesized by the polymerization of colloidal silica-entrapped resorcinol/formaldehyde in the presence of ammonia as catalyst, followed by carbonization, sodium hydroxide (NaOH) etching to remove silica template, and potassium hydroxide (KOH) activation. The morphology and microstructure are characterized by scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption–desorption. The results show that a typical sample (denoted as MMCS-3) unites the characteristics of regular spherical shape (uniform diameters of 500 nm), high specific surface area (1,620 m² g^?1), large pore volume (1.037 cm³ g^?1), and combined micropores and mesopores (11.0 nm), which endows MMCS-3 good electrochemical performance. MMCS-3 as supercapacitor electrode shows a specific capacitance of 314 F g^?1 under a current density of 0.5 A g^?1 and low internal resistance of 0.2 Ω in 6 M KOH aqueous solution. The electrochemical capacitance still retains 198 F g^?1 at a high current density of 10 A g^?1. After 500 cycle numbers of galvanostatic charge/discharge at 0.5 A g^?1, MMCS-3 electrode still remains the specific capacitance of 301 F g^?1 with the retention of 96 %. This study highlights the potential of well-designed MMCSs as electrodes for widespread supercapacitor applications.     

Hierarchical nanocomposites of polyaniline scales coated on graphene oxide sheets for enhanced supercapacitors

The homogeneous polyaniline–graphene oxide (PANI-GO) nanocomposites were facilely assembled with a redox system in which cumene hydroperoxide (CHP) and iron dichloride (FeCl₂) acted as oxidant and reductant, respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images showed that PANI scales coated uniformly on the surface of GO sheets owing to the synergistic effect between the PANI and GO. The obtained PANI-GO nanocomposites exhibited improved electrochemical performance as an electrode material for supercapacitors compared with the pure PANI. The specific capacitance of the PANI-GO nanocomposites was high up to 308.3 F g^?1, much higher than that of the pure PANI with specific capacitance of 150 F g^?1 at a current density of 1 A g^?1 in 2 M H₂SO₄ electrolyte. The Raman and XPS results illustrated that enhanced electrochemical performance might be attributed to the π-π conjugation between the PANI and GO sheets.     

Water-in-oil microemulsion method preparation and capacitance performance study of Li4Mn5O12

Spinel Li₄Mn₅O₁₂ nanoparticles are successfully prepared by water-in-oil microemulsion method and characterized by X-ray diffraction and scanning electron microscopy. The Li₄Mn₅O₁₂ nanoparticles have sphere-like morphology with particle size less than 50 nm. The Li₄Mn₅O₁₂ and activated carbon (AC) were used as electrodes of Li₄Mn₅O₁₂/AC supercapacitor, respectively. The electrochemical capacitance performance of the supercapacitor was investigated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The results showed that the single electrode was able to deliver specific capacitance 252 F g^?1 within potential range 0–1.4 V at a scan rate of 5 mV s^?1 in 1 mol L^?1 Li₂SO₄ solution, and it also showed high coulombic efficiency close to 100%. This material exhibited a good cycling performance.     

Design of high-performance core-shell hollow carbon nanofiber@nickel-cobalt double hydroxide composites for supercapacitive energy storage

The supercapacitive performances of supercapacitor mainly depend on the physical nanostructure and micro-morphology of electrode materials. Here, we demonstrated the design, synthesis and electrochemical performances of core-shell hollow carbon nanofiber@nickel-cobalt-layered double hydroxide (HCNF@ Ni_0.67Co_0.33-LDH) nanocomposites with an optimized Ni/Co molar ratio of 2:1. The HCNF was used as superiorly conductive core to sustain the nanoporous silky Ni_0.67Co_0.33-LDH shell, which can efficiently provide fast transport pathways for electrons and electrolyte ions. The outstanding specific capacitance of 2486 F g^?1 at 1 A g^?1 based on galvanostatic charge-discharge curves were acquired for the highly electroactive HCNF@Ni_0.67Co_0.33-LDH. Furthermore, the HCNF@Ni_0.67Co_0.33-LDH electrode delivered a distinguished rate capability with a specific capacitance of 1890 F g^?1 even at 15 A g^?1. Notably, an asymmetric supercapacitor with HCNF@Ni_0.67Co_0.33-LDH as cathode and HCNF as anode was devised, which presented a prominent specific capacitance of 228 F g^?1, good energy density of 62.1 Wh kg^?1, and impressive cycling stability (90.6% capacitance retention after 10,000 cycles).     

Co-electrodeposition of MnO2/graphene oxide coating on carbon paper from phosphate buffer and the capacitive properties

MnO₂/graphene oxide sheet composite (MnO₂/GOS) has been co-electrodeposited on the thermally treated carbon paper (TTCP) in phosphate buffer solution containing GOS and KMnO₄. The resulted samples have been characterized by scanning and transmission electron microscopy, Raman, X-ray diffraction, and X-ray photoelectron energy spectroscopy. The results show that the synthesized MnO₂ may be δ-MnO₂ and the morphology of MnO₂/GOS is very different from that of MnO₂, indicating that the introduction of GOS in electrolyte can influence the morphology during the deposition. The capacitive properties of the samples are investigated by using cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The specific capacitance of MnO₂ for MnO₂/GOS can reach about 829 F g^?1 at discharged current density of 1.0 A g^?1 in 1 M Na₂SO₄ aqueous solution, which is larger than that of MnO₂ deposited on TTCP. The composite of MnO₂/GOS also exhibits excellent cyclic stability with a decrease of 18.5 % specific capacitance after 1,500 cycles.     

Supercapacitive performance of homogeneous Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/TiO<Subscript>2</Subscript> nanotube arrays enhanced by carbon layer and oxygen vacancies

Self-supported and binder-free electrodes based on homogeneous Co₃O₄/TiO₂ nanotube arrays enhanced by carbon layer and oxygen vacancies (Co₃O₄/co-modified TiO₂ nanotube arrays (m-TNAs)) are prepared via a simple and cost-effective method in this paper. The highly ordered TNAs offer direct pathways for electron and ion transport and can be used as 3D substrate for the decoration of electroactive materials without any binders. Then, by a facile one-step calcination process, the electrochemical performance of the as-obtained carbon layer and oxygen vacancy m-TNAs is approximately 83 times higher than that of pristine TNAs. In addition, Co₃O₄ nanoparticles are uniformly deposited onto the m-TNAs by a universal chemical bath deposition (CBD) process to further improve the supercapacitive performance. Due to the synergistic effect of m-TNAs and Co₃O₄ nanoparticles, a maximum specific capacitance of 662.7 F g^?1 can be achieved, which is much higher than that of Co₃O₄ decorated on pristine TNAs (Co₃O₄/TNAs; 166.2 F g^?1). Furthermore, the specific capacitance retains 86.0 % of the initial capacitance after 4000 cycles under a high current density of 10 A g^?1, revealing the excellent long-term electrochemical cycling stability of Co₃O₄/m-TNAs. Thus, this kind of heterostructured Co₃O₄/m-TNAs could be considered as promising candidates for high-performance supercapacitor electrodes.     

Mechanochemically prepared polyaniline and graphene-based nanocomposites as electrodes of supercapacitors

Conductive nanocomposites based on polyaniline and graphene (PAni/Gr) were prepared by cheap and efficient mechanochemical method. The uniform distribution of Gr nanoparticles in the polymer matrix and the ordering of the polymer chains due to the action of mechanical shear stresses, which were established by TEM, stipulated high specific capacitance about 920 F g^?1 in ??0.2–1.0 V vs. Ag/AgCl potential range. PAni/Gr-based electrodes are able to provide the specific capacitance of ~?750 F g^?1 at 2 A g^?1 in symmetric supercapacitors (SSC) and stably cycle at the operating voltage V?=?0.65 V for 10,000 charge-discharge cycles with 96% capacitance retention, whereas the increasing of V leads to the loss of stability as a result of the cathode degradation. PAni/Gr-based SSC possessed improved self-discharge showed high rate capability, and the specific power of such SSC could reach ~?10 kW kg^?1 at the specific energy of ~?18 W h kg^?1.     

Nanostructured ferrite/graphene/polyaniline using for supercapacitor to enhance the capacitive behavior

Graphene nanosheets, polyaniline (PANI), and nanocrystallites of transition metal ferrite {Fe₃O₄ (Mag), NiFe₂O₄ (NiF), and CoFe₂O₄ (CoF)} have been prepared and characterized via XRD, FTIR, SEM, TEM, UV–vis spectroscopy, cyclic voltammetry, galvanostatic charge discharges, and impedance spectroscopy. Electrochemical measurements showed that supercapacitances of hybrid electrodes made of the ternary materials are higher than that of hybrid electrode made of binary or single material. The ternary hybrid CoF/graphene (G)/PANI electrode exhibits a highest specific capacitance reaching 1123 Fg^?1, an energy density of 240 Wh kg^?1 at 1 A g^?1, and a power density of 2680 Wkg^?1 at 1 A g^?1 and outstanding cycling performance, with 98.2% capacitance retained over 2000 cycles. The extraordinary electrochemical performance of the ternary CoF/G/PANI hybrid can be attributed to the synergistic effects of the individual components. The PANI conducting polymer enhances an electron transport. The Ferrite nanoparticles prevent the restocking of the carbon sheets and provide Faradaic processes to increase the total capacitance.