Electrochemically synthesized graphene/polypyrrole composites and their use in supercapacitor

Composite films consisting of polypyrrole (PPy) and graphene oxide (GO) were electrochemically synthesized by electrooxidation of 0.1 M pyrrole in aqueous solution containing appropriate amounts of GO. Simultaneous chronoamperometric growth profiles and frequency changes on a quartz crystal microbalance showed that the anionic GO was incorporated in the growing GO/PPy composite to maintain its electrical neutrality. Subsequently, the GO was reduced electrochemically to form a reduced GO/PPy (RGO/PPy) composite by cyclic voltammetry. Specific capacitances estimated from galvanostatic discharge curves in 1 M H₂SO₄ at a current density of 1 A g^?1 indicated that values for the RGO/PPy composite were larger than those of a pristine PPy film and the GO/PPy composite. In the case of 6 mg mL^?1 GO for the preparation of GO/PPy, a high specific capacitance of 424 F g^?1 obtained at the electrochemically prepared RGO/PPy composite indicated its potential for use as an electrode material for supercapacitors.     

Electrochemical behaviors of graphene-ZnO and graphene-SnO2 composite films for supercapacitors

Graphene, graphene-ZnO and graphene-SnO₂ films were successfully synthesized and used as electrode materials for electrochemical supercapacitors, respectively. The screen-printing approach was employed to fabricate graphene film on graphite substrate while the ZnO and SnO₂ were deposited on graphene films by ultrasonic spray pyrolysis. The electrochemical performances of these electrodes were comparatively analyzed through electrochemical impedance spectrometry, cyclic voltammetry and chronopotentiometry tests. The results showed that the incorporation of ZnO or SnO₂ improved the capacitive performance of graphene electrode. Graphene-ZnO composite electrode exhibited higher capacitance value (61.7 F/g) and maximum power density (4.8 kW/kg) as compared with graphene-SnO₂ and pure graphene electrodes.     

Electrochemical properties of microwave-assisted reflux-synthesized Mn<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles in different electrolytes for supercapacitor applications

The nanosized Mn₃O₄ particles were prepared by microwave-assisted reflux synthesis method. The prepared sample was characterized using various techniques such as X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), Raman analysis, and transmission electron microscopy (TEM). Electrochemical properties of Mn₃O₄ nanoparticles were investigated using cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge–discharge analysis in different electrolytes such as 1 M KCl, 1 M Na₂SO₄, 1 M NaNO₃, and 6 M KOH electrolytes. XRD pattern reveals the formation of single-phase Mn₃O₄ nanoparticles. The FT-IR and Raman analysis also assert the formation of Mn₃O₄ nanoparticles. The TEM image shows the spherical shape particles with less than 50 nm sizes. Among all the electrolytes, the Mn₃O₄ nanoparticles possess maximum specific capacitance of 94 F g⁻¹ in 6 M KOH electrolyte calculated from CV. The order of capacitance obtained by various electrolytes is 6 M KOH > 1 M KCl > 1 M NaNO₃ > 1 M Na₂SO₄. The EIS and galvanostatic charge–discharge results further substantiate with the CV results. The cycling stability of Mn₃O₄ electrode reveals that the prepared Mn₃O₄ nanoparticles are a suitable electrode material for supercapacitor application.     

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.     

Manganese oxide precipitated into activated carbon electrodes for electrochemical capacitors

Manganese oxide was prepared at different pH and temperatures and then precipitated into activated carbon by the chemical impregnation method. Size distributions of manganese oxide sol were also measured by light scattering. The electrodes were annealed in nitrogen gas at different temperatures. In addition, electrochemical characterization was carried out using cyclic voltammetry (CV) at a scan rate of 25 mV s⁻¹ and chronopotentiometry (CP) with constant-current (10 mA cm⁻²). Maximum capacitance of 461.3 F g⁻¹ was obtained in a 0.1 M Na₂SO₄ solution for manganese oxide prepared under optimum conditions (pH = 13.11 and T = 25 oC) and annealed at a temperature of 195 oC. The manganese oxide particle size decreased with annealing. This probably leads to increased specific capacitance. Using X-ray photoelectron spectroscopy (XPS) the results reveal that manganese oxide species are transformed from hydroxide to oxide after annealing.     

Electrocatalytic activity of electrodeposited composite films of polypyrrole and CoFe2O4 nanoparticles towards oxygen reduction reaction

Electrochemical behaviour of sandwich-type composite electrodes of polypyrrole (PPy) and CoFe₂O₄ nanoparticles (Ox) were investigated in an aqueous solution of 0.5 M K₂SO₄ and 5mM KOH at 25 °C using electrochemical impedance (EI), cyclic voltammetry (CV) and Tafel polarization techniques. EI and CV studies indicated that the incorporation of oxide nanoparticles influenced the charge transfer and transport behaviours of the polymer matrix greatly. The bulk electrical resistances of pure polymer (4.5 ± 1.7 Ω) as well as composite (2.7 ± 0.8 Ω) electrodes were practically constant in the potential region, +0.1 to −0.7 V. The latter electrode showed a good electrocatalytic activity towards the oxygen reduction reaction (ORR).     

Facile synthesis and electrochemical capacitance of composites of polypyrrole/multi-walled carbon nanotubes

Composites of polypyrrole (PPy) and multi-walled carbon nanotubes (MWCNTs) were synthesized by a facile method involving one-step electrochemical deposition from a thin-layer of ionic liquid solution attached on a glassy carbon electrode. The morphology of the composites was characterized by field emission scanning electron microscopy, and the capacitance properties were investigated by cyclic voltammetry (CV). The charge-discharge behavior of the composites prepared in this work was examined by chronopotentiometry at a constant current density for multi-cycle scans. The results show that the PPy/MWCNT composites have a porous 3D nanostructure, with high specific capacitance (SC) of 890 F/g (for the mass of the PPy in the composites) calculated from CV at 2 mV/s in 1.0 M KCl. The stability of the composites in 1.0 M KCl electrolyte was also examined by multi-cycle CV and only 9% decrease of SC value was observed for the 1000 cycles.     

Polypyrrole and La1−xSrxMnO3 (0≤ x ≤0.4) composite electrodes for electroreduction of oxygen in alkaline medium

Composite G/PPy/PPy(La_1−xSr_xMnO₃)/PPy electrodes made of the perovskite La_1−xSr_xMnO₃ embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La_1−xSr_xMnO₃) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm⁻³ pyrrole (Py) plus 0.05 mol dm⁻³ K₂SO₄ with and without containing a suspension of 8.33 g L⁻¹ oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm⁻³ K₂SO₄ plus 5 mmol dm⁻³ KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.     

Ethanol electrooxidation on platinum particles dispersed on poly(neutral red) film

The conductive polymer poly(neutral red) polymerized on a graphite electrode (PNR/graphite) as a support material was used for catalytic oxidation of ethanol in acidic solution and investigated by electrochemical methods. Pt particles loaded on the surface of PNR/graphite electrode exhibited higher electrocatalytic activity for ethanol oxidation in comparison with Pt particles supported directly on graphite. With the equivalent loading mass of Pt catalyst, the special activity (S _A ) at peak a of the Pt/PNR/graphite electrode polymerized for 10 cycles in 5 × 10⁻⁴ M NR + 0.5 M H₂SO₄ solution is 3,478 A C⁻¹ and about 2.20 times higher than that of the Pt/graphite electrode (1,582 A C⁻¹). The results show that the electrochemical performance of Pt catalyst for ethanol oxidation is improved by the addition of PNR     

Electrochemical characterization of carbon nanotubes as electrode in electrochemical double-layer capacitors

Carbon nanotubes uniformly 50 nm in diameter were directly grown on graphite foil. Cyclic voltammetry (CV) shows that the carbon nanotube/graphite foil electrode has a high specific capacitance (115.7 F/g at a scan rate of 100 mV/s) and exhibits typical double-layer behavior. A rectangular-shaped CV curve persists even at a scan rate of 100 mV/s in 1.0 M H₂SO₄ aqueous solution, which suggests that the carbon nanotube electrode could be an excellent candidate as the electrode in electrochemical double-layer capacitors. In addition, the influence of the potential scan rate, aging, and the electrolyte solution on the specific capacitance of nanotube electrodes was also studied.     

Capacitive behavior of polycarbazole- and poly(N-vinylcarbazole)-coated carbon fiber microelectrodes in various solutions

The electrochemical behavior of polycarbazole (PCz) and poly(N-vinyl carbazole) P(NVCz) was investigated by means of electrochemical impedance spectroscopy (EIS). Supporting electrolytes made from various combinations of solvents (acetonitrile and propylene carbonate) and salts (sodium perchlorate, lithium perchlorate, and tetraethyl ammonium perchlorate) were employed in the investigation. Information on the double layer capacitance (C_dl) and specific capacitance (C_sp) of P(NVCz) was achieved by cyclic voltammetry (CV), chronoamperometry and chronopotentiometry. Carbon fiber microelectrodes (CFME) were electrocoated by cyclic voltammetry in a monomer-free solution and displayed film thicknesses in the range ~200 nm to ~4.8 μm. The capacitive behavior of the PCz- and P(NVCz)-coated carbon fiber microelectrodes was also investigated by CV. The effects of the type of electrolyte and solvent on the electrochemical impedance spectroscopic data were subsequently fitted with an ((R(C(R(Q(RW))))(CR))-equivalent circuit model to calculate the numerical values of the proposed components. The obtained experimental C_sp values for PCz/CFME and P(NVCz)/CFME, as measured in LiClO₄/ACN, were 280.5 mF g⁻¹ and 294.1 mF g⁻¹, respectively.     

Preparation and characterization of manganese oxide/CNT composites as supercapacitive materials

Manganese oxide was synthesized and dispersed on carbon nanotube (CNT) matrix by thermally decomposing manganese nitrates. CNTs used in this paper were grown directly on graphite disk by chemical vapor deposition technique. The capacitive behavior of manganese oxide/CNT composites was investigated by cyclic voltammetry and galvanostatic charge–discharge method in 1 M Na₂SO₄ aqueous solutions. When the loading mass of MnO₂ is 36.9 μg cm^− 2, the specific capacitance of manganese oxide/CNT composite (based on MnO₂) at the charge–discharge current density of 1 mA cm^− 2 equals 568 F g^− 1. Additionally, excellent charge–discharge cycle stability (ca. 88% value of specific capacitance remained after 2500 charge–discharge cycles) and power characteristics of the manganese oxide/CNT composite electrode can be observed. The effect of loading mass of MnO₂ on specific capacitance of the electrode has also been investigated.     

Electrochemical fabrication of polyaniline/MnO2/graphite felt as free‐standing,flexible electrode for supercapacitors

Polyaniline/MnO₂/graphite felt (PMGF) composite, which can be used as a novel free‐standing, flexible electrode for supercapacitors, was fabricated via a facile electrochemical method. Polyaniline/graphite felt (PANI/GF) electrode was prepared by electropolymerization of PANI onto the GF. Subsequently, manganese dioxide (MnO₂) was electrodeposited on the surface of the PANI/GF electrode to prepare PMGF electrode. The microstructure and morphology of the as‐prepared samples were characterized by Fourier transform infrared spectra, X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. Specific surface area was examined using N₂ adsorption/desorption test. Cyclic voltammogram, chronopotentiometry techniques and electrochemical impedance spectroscopy were introduced to investigate the electrochemical performance of the composites. The PMGF electrode exhibited specific capacitance as high as about 630 F g⁻¹ at the current density of 0.5 A g⁻¹, which is much higher than that of PANI/MnO₂ composites reported previously. The high specific capacitance of PMGF may be attributed to the fact that the porous GF is a good conductive matrix for the dispersion of PANI/MnO₂ and it can facilitate easy access of electrolytes to the electrode, which results in enhancement of the electrochemical performance of the composite. Moreover, the specific capacitance of PMGF is much larger than that of MnO₂/GF (MGF), which may be ascribed to the participant of PANI, which contributes additional pseudocapacitance and electron transport path. POLYM. COMPOS., 34:819–824, 2013. © 2013 Society of Plastics Engineers     

Hydrothermal synthesis of Polypyrrole/MoS2 intercalation composites for supercapacitor electrodes

As a pseudocapacitive electrode materials for supercapacitor, Polypyrrole (PPy) exhibit excellent theoretical specific capacitance. However, it suffers from a poor cycling stability due to structural instability during charge-discharge process. In this work, a novel and facile hydrothermal method has been developed for the intercalation composites of PPy/MoS₂ with multilayer three-dimensional structure. The report result shows that the as-prepared electrode possess a outstanding electrochemical properties with significantly specific capacitance of 895.6 F g⁻¹ at current density of 1 A g⁻¹, higher energy density (3.774 Wh kg⁻¹) at power density of 252.8 kW kg⁻¹, furthermore, it also achieve remarkable cycling stability (~98% capacitance retention after 10,000 cycles) which is attributed to the synergistic effect of PPy and MoS₂. This synthetic strategy integrates performance enables the multilayer PPy/MoS₂ composites to be a promising electrode for energy storage applications.     

Supercapacitive properties of composite electrodes consisting of polyaniline, carbon nanotube, and RuO2

Three types of composite supercapacitor electrodes were prepared; electroactive polyaniline (PANI), PANI/multi-walled carbon nanotube (CNT), and PANI/CNT/RuO₂. Specifically, the PANI and PANI/CNT were prepared by polymerization, and PANI/CNT/RuO₂ was prepared by electrochemical deposition of RuO₂ on the PANI/CNT matrix. Cyclic voltammetry between −0.2 and 0.8 V (vs. Ag/AgCl) at various scan rates was performed to investigate the supercapacitive properties in an electrolyte solution of 1.0 M H₂SO₄. The PANI/CNT/RuO₂ electrode showed the highest specific capacitance at all scan rates (e.g., 441 and 392 F g⁻¹ at 100 and 1,000 mV s⁻¹, respectively). In contrast, the PANI/CNT electrode demonstrated the best capacitance retention (66%) after 10⁴ cycles. Additional analysis including morphology and complex impedance spectroscopy suggested that with small loading of RuO₂, an increase in capacitance was observed, but dissolution and/or detachment of RuO₂ species from the electrode might occur during cycling to reduce the cycle performance.     

Electrophoretic deposition of MnO2-coated carbon nanotubes on a graphite sheet as a flexible electrode for supercapacitors

A flexible electrode was prepared by microwave heating deposition of manganese oxide (MnO₂) on carbon nanotubes (CNTs) followed by electrophoretic deposition of the MnO₂-coated CNTs on a flexible graphite sheet (FGS). The prepared MnO₂-coated CNTs were characterized by scanning and transmission electron microscopy, and X-ray diffraction. A uniformly thin nano-scale MnO₂ coating was formed on the surface of the CNTs. The MnO₂-coated CNTs–FGS electrode showed highly capacitive behaviour in the 0.5 M Na₂SO₄ aqueous solution, with a specific capacitance of 442.9 F/g based on MnO₂ at 2 mV/s. It exhibited an excellent cycling stability with no more than 1.1% capacitance loss after 1000 cycles at 50 mV/s.     

Synthesis of polypyrrole-reduced graphene oxide composites by in-situ photopolymerization and its application as a supercapacitor electrode

A highly conductive polypyrrole (PPy)-reduced graphene oxide (RGO) composite with an electrical conductivity of 610 S m⁻¹ was successfully synthesized by the in-situ photopolymerization of pyrrole in a graphene oxide suspension. Graphene oxide (GO) played the role of an electron acceptor and was reduced as it accepted electrons. The reduction of GO was confirmed by the increase in the C/O ratio of RGO with the UV irradiation time as well as the high electrical conductivity of PPy-RGO composite. Through the thermogravimetric analysis, it has been found that the PPy-RGO composite exhibited high thermal stability compared to the GO and PPy. This material was used as an electrode in a supercapacitor cell and showed excellent performance for electrical energy storage. The composite exhibited a specific capacitance of 376 F g⁻¹ at a scan rate of 25 mV s⁻¹.     

Effect of calcination temperature on structural,morphological and electrochemical properties of Sn doped Co3O4 nanorods

Tremendous attention has been devoted for the development of highly efficient and stable electrode materials for supercapacitor applications. In this study, Sn-doped Co₃O₄ nanorods were prepared via solvothermal process using PVP and oxalic acid as surfactants. The phase, morphology and composition of Sn-doped Co₃O₄ nanorods were examined by XRD and SEM/EDX techniques. The electrochemical properties were studied via cyclic voltammetry (CV), galvanostatic charging-discharging (GCD), electrochemical impedance spectroscopy (EIS) measurements. The CV results show that electrode based on 5 at. % Sn-doped Co₃O₄ (5Sn-doped Co₃O₄) nanorods delivered the highest specific capacitance (842.44 F/g) at 5 mV/s than that of the electrode based on pure Co₃O₄ (729.39 F/g). In order to further tune the performance of this electrode, the structure, morphology and electrochemical behavior of 5Sn-doped Co₃O₄ sample were optimized via variety of calcination temperatures ranging from 250 to 400 °C. Notably, the 5Sn-doped Co₃O₄ sample calcined at 350 °C exhibited higher electrochemical performance (specific capacitance ~913.10 F/g) than other samples calcined at low or high calcination temperatures. The CV curves of 5Sn-doped Co₃O₄/T-350 °C at scan rates of 5–35 mV/s also showed pseudocapacitor behavior and good electrochemical reversibility. Moreover, the prepared novel electrode material has also displayed good rate capability (71.77%) at current density of 1–10 A/g and long-term stability of 92.23% after 3000 cycles. These excellent electrochemical characteristics of 5Sn–Co₃O₄/T-350 °C nanorods verified that it will be highly suitable electrode material for supercapacitor applications.     

Wet chemical synthesis of Gd+3 doped vanadium Oxide/MXene based mesoporous hierarchical architectures as advanced supercapacitor material

In this paper, Gd³⁺ doped V₂O₅/Ti₃C₂T_x MXene (GVO/MX) hierarchical architectures have been synthesized by wet chemical approach. As prepared GVO/MX composite, along undoped VO and unsupported GVO were well characterized by XRD, FESEM, EDX, FT-IR and BET techniques. Electrochemical performance of VO, GVO and GVO/MX was evaluated by CV, GCD and EIS measurements. Among the three electrodes, GVO/MX composite exhibited highest electrochemical activity with the optimum specific capacitance of 1024 Fg^-1 at 10 mVs^?1. The specific capacitance of GVO/MX was ～1.7 and ～3 times higher than unsupported GVO (585 Fg^-1) and VO (326 Fg^-1), respectively. The cyclic life of GVO/MX with capacitance retention 96.12% was observed at 60 mVs^?1. EIS measurements showed reduction in electrochemical impedance for GVO/MX as compared to GVO and VO. The corresponding impedance values of Rct and Resr for GVO/MX were calculated as 18 Ω and 1.8 Ω, respectively. The superior capacitive ability of GVO/MX can be ascribed to its unique morphology, short diffusion path and high surface area of fabricated composite. Considering it, the present work provides a feasible strategy to fabricate highly effective electrode materials for next generation energy storage devices.     

Anodic oxidation of organic pollutants on a Ti/SnO<Subscript>2</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>4</Subscript> anode

A Ti/SnO₂–Sb₂O₄ electrode was prepared by alternate Sn and Sb electrodepositions using the thermo-electrochemical method. The chemical, electrochemical, and structural characterization of the electrode was performed and it was tested in the anodic oxidation of several pollutants, phenol, ibuprofen, acid orange 7 (AO7), and diclofenac, all in aqueous 0.035 M Na₂SO₄ solutions at current densities of 10 and 20 mA cm⁻². After the 24 h assay, removal of chemical oxygen demand, total organic carbon (TOC) and absorbance were very high, especially at the higher current density. TOC removals presented the lowest value. However, after 24 h at 20 mA cm⁻², TOC removals were: phenol—94%; ibuprofen—83%; AO7—88%; and diclofenac—73%. Combustion efficiency and instantaneous and mineralization current efficiencies were also determined.