WO2015016700A1 - Procédé de préparation assistée par catalyseur d'un film de graphène décoré de nanoparticules de polypyrrole pour supercondensateur haute performance - Google Patents

Procédé de préparation assistée par catalyseur d'un film de graphène décoré de nanoparticules de polypyrrole pour supercondensateur haute performance Download PDF

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WO2015016700A1
WO2015016700A1 PCT/MY2014/000054 MY2014000054W WO2015016700A1 WO 2015016700 A1 WO2015016700 A1 WO 2015016700A1 MY 2014000054 W MY2014000054 W MY 2014000054W WO 2015016700 A1 WO2015016700 A1 WO 2015016700A1
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solution
graphite oxide
ppy
deposition
electrode
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Hong Ngee LIM
Nay Ming HUANG
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Universiti Putra Malaysia
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • Embodiments of the present invention generally relate to graphene materials, and more particularly, to methods for preparing catalyst-assisted polypyrrole nanoparticles decorated graphene film and suitable for use in electrochemical devices such as supercapacitors.
  • Background Art :
  • Graphene is a two-dimensional planar allotrope of carbon in which carbon atoms are formed in a honeycomb lattice structure, and has a high charge mobility of about 20,000-50,000 cm/Vs and a very high theoretical specific surface area of 2,630 m 2 /g.
  • SCs supercapacitors
  • graphene is light, highly flexible and mechanically strong (resisting tearing by AFM tips), and the material's dense atomic structure makes it impermeable to gases.
  • the combination of high electrical conductivity, good mechanical properties, high surface area, and low manufacturing cost make graphene an ideal candidate material for electrochemical applications.
  • Graphene oxide obtained through treating graphite with a strong oxidizer, whose basal planes and edges are abundant with various oxygen-containing group, has also attracted great interest recently.
  • the oxygen-containing groups such as epoxy, hydroxyl, ether and carbonyl promote good solubility in polar solvent and render versatility for the construction of GO-based hybrid nanocomposites, hence, expanding their potential applications.
  • Recently, methods of utilizing graphene resulting from such oxidation-reduction as the electrodes of supercapacitors ⁇ or ultracapacitors) have been devised, by which the fabrication of supercapacitors having a specific capacitance of about 80 F/g or more has been reported. (R. S. Ruoff, Nano Left., 2008, 8 (10), pp 3498-3502).
  • SCs supercapacitors
  • batteries have increased greatly mainly due to the demand for power systems with high energy and power densities.
  • energy storage devices such as supercapacitors (SCs) and batteries
  • SCs supercapacitors
  • supercapacitors (SCs) are considered promising candidate for applications ranging from electric vehicles to cellular phones.
  • SCs have received considerable attention due to its expanding arrays of application since portable electronics continue to gain in popularity.
  • SCs supercapacitors
  • electrode materials i.e. carbon materials, metal oxides/hydroxides and conducting polymers.
  • Conducting polymers such as polypyrrole (PPy) have been studied in great detail over the years because of their unique metal-like electrical properties as well as highly desirable polymeric characteristic such as flexibility, low density, and ease of structural modification, lead to many new possibilities for device fabrication.
  • electrochemical copolymerization onto a substrate may be one of the best ways to fabricate electrode materials.
  • electrochemical copolymerization with GR suffer from polymeric aggregation where the polymer often blocks electrolyte channels on the outer surface forming a dense polymer layer that completely envelopes GR sheets. This leads to high electrode resistance due to poor interconnection between conductivity structures. Due to the dense layer of polymer on the surface of the composite film, penetration of electrolyte into the bulk of the composite material is very difficult.
  • Embodiments of the present invention aim to provide a method for preparing polypyrrole and graphene nanocomposite films, and the method includes the steps of: providing a graphite source and oxidizing the graphite source to form graphite oxide solution, washing the graphite oxide solution for thickening the graphite oxide solution, creating a dispersion of the graphite oxide solution in a liquid, thickening the graphite oxide solution to form a graphite oxide gel, introducing at least one reagent into an one- compartment cell, providing a deposition solution and dipping it in the graphite oxide gel, stirring the deposition solution for a particular time period, reacting the at least one reagent to form polypyrrole within the deposition solution, providing a substrate, and applying an electric field across at least a portion of the deposition solution dipped in the graphite oxide gel for depositing at least one portion of graphene from the graphite oxide gel and the deposition solution on the substrate to form polypyrrole and graphene nanocompo
  • the invention aim to provide a catalyst-assisted polypyrrole nanoparticles decorated on graphene film.
  • the nanocomposite film prepared by a method includes the steps of providing a graphite source and oxidizing the graphite source to form graphite oxide solution, washing the graphite oxide solution for thickening the graphite oxide solution, creating a dispersion of the graphite oxide solution in a liquid, thickening the graphite oxide solution to form a graphite oxide gel, introducing at least one reagent into an one-compartment cell, providing a deposition solution and dipping it in the graphite oxide gel, stirring the deposition solution for a particular time period, reacting the at least one reagent to form polypyrrole within the deposition solution, providing a substrate, and applying an electric field across at least a portion of the deposition solution dipped in the graphite oxide gel for depositing at least one portion of graphene from the graphite oxide gel and the deposition solution
  • the word “may” is used in a permissive sense (i.e., meaning having the potential to), rather than the mandatory sense (i.e., meaning must).
  • the words “include,” “including,” and “includes” mean including, but not limited to.
  • the words “a” or “an” mean “at least one” and the word “plurality” means one or more, unless otherwise mentioned.
  • FIG.1 is an illustration of FESEM images of the surface of (a) C-PPy, (b) PPy, (c) 1.0 mM Fe C-PPy/GR, (d) Cross sectional view of 1.0 mM Fe C-PPy/GR, (e) High magnification of (d), and (f) HRTEM image of 1.0 mM Fe C-PPy/GR, according to an embodiment of the present invention;
  • FIG.2A is a schematic diagram illustrating a potentiostatic electropolymerization (continuous deposition) process and FIG.2B is a schematic diagram illustrating a whole catalyst-assisted electropolymerization process, according to an embodiment of the present invention
  • FIG.3 is a graphical illustration of FESEM images of the (a) top view of PPy/GR, (b) cross sectional view of PPy/GR, (c) top view of 0.25 mM Fe C-PPy/GR, (d) cross sectional view of 0.25 mM Fe C-PPy/GR, (e) top view of 0.5 mM Fe C-PPy/GR and (f) cross sectional view of 0.5 mM Fe C-PPy/GR, according to an embodiment of the present invention;
  • FIG.4A is a graphical illustration of wide scans of GO, C-PPy, and C-PPy/GR nanocomposite film
  • FIG.4B is a graphical illustration of de-convoluted XPS spectra of GO, C-PPy, and C-PPy/GR nanocomposite film, according to an embodiment of the present invention
  • FIG.5 is a graphical illustration of XRD pattern of GO, PPy, PPy/GR and C- PPy/GR, according to an embodiment of the present invention
  • FIG.6 is a graphical illustration of Raman spectra of GO, C-PPy and C- PPy/GR, according to an embodiment of the present invention.
  • FIG.7 is a graphical illustration of FT-IR spectra of GO and C-PPy/GR according to an embodiment of the present invention.
  • FIG.8A is a graphical illustration of CVs for PPy, C-PPy, PPy/GR, 0.25 mM Fe C- PPy/GR, 0.5 mM Fe C-PPy/GR and 1.0 mM Fe C-PPy/GR at a scan rate of 2 mV/s
  • FIG.8B CVs of 1.0 mM Fe C-PPy/GR nanocomposite at various scan rate (100-2 mV/s), according to an embodiment of the present invention
  • FIG.9 is a graphical illustration of Galvanostatic charge/discharge curves for the 1.0 mM Fe C-PPy/GR, PPy/GR, C-PPy and PPy electrodes for comparison at a current density of 1 A/g, according to an embodiment of the present invention
  • FIG.10 Nyquist plot of C-PPy/GR and PPy/GR, according to an embodiment of the present invention.
  • FIG.11 Specific capacity retention for 1.0 mM C-PPy/GR and PPy/GR electrodes at charge/discharge current density of 1 A/g, according to an embodiment of the present invention.
  • Various embodiments of the present invention aim to provide a method to control the particle size of polypyrrole coated on individual graphene using a catalyst-assisted electrochemical deposition technique for supercapacitor electrode.
  • the present method provides synthesis of catalyst-assisted polypyrrole/graphene (C-PPy/GR) nanocomposite potentiostatically with the addition of FeCI 3 catalyst to the deposition setup with differing catalyst amount used in an effort to control the size of pyrrole on graphene for homogenous coating and avoid polymeric aggregation aimed for synergistic capacitive ability.
  • C-PPy/GR catalyst-assisted polypyrrole/graphene
  • the main objective of present invention is to prepare an optimized homogenous C-PPy/GR nanocomposite film that provides high performance to be utilized for supercapacitor application.
  • nanocomposite film nano-size PPy disperse homogeneously on the GR, preventing restacking of the GR layer that offers a unique three-dimensional open structure which facilitates diffusion of electrolyte, resulting in impressive electrochemical properties.
  • the method includes the steps of, applying the electric field includes providing an electrophoresis solution includes a supporting electrolyte, and forming the graphene-based conducting nanocomposite film on a surface of the substrate.
  • the nanocomposite film is formed on the surface of the substrate by simultaneously depositing the at least one portion of the deposition solution and the at least one portion of graphene from the graphite oxide gel onto the surface of the substrate by an electrophoresis deposition (EPD) method in a proper electrophoresis deposition (EPD) condition.
  • the step of forming of the nano-composite film includes electro-chemical processing and the time period is about 30 minutes to allow polypyrrole to form in the deposition solution.
  • the deposition solution includes a conductive polymer.
  • the electro-chemical processing includes installing a three electrode cell by connecting a saturated calomel electrode as a reference electrode, a graphite electrode as a counter electrode, an indium tin oxide (ITO) electrode as a working electrode, and submerging an electrode cell into the deposition solution.
  • a saturated calomel electrode as a reference electrode
  • a graphite electrode as a counter electrode
  • ITO indium tin oxide
  • the electrophoresis deposition (EPD) step is performed by a potentiostatic method.
  • the potentiostatic method includes applying a potential of about +0.8 V for about two hours for depositing the deposition solution onto the surface of the substrate at room temperature.
  • the reagent includes metal catalyst and the metal catalyst is Iron (III) chloride.
  • the conductive polymer is a polypyrrole and a supporting electrolyte is a sodium p-toluenesulfonate.
  • the substrate has an active surface and the active surface is conductive.
  • the active surface is selected from graphite, Indium-Tin-Oxide (ITO), glass, which may or may not be coated with a metal.
  • ITO Indium-Tin-Oxide
  • the active surface is selected from an electrode and a metal (or alloy) coated glass.
  • the liquid is an acid solution and the acid solution is hydrochloric acid.
  • concentration of the graphite oxide gel is about 4.38 mg/ml.
  • the deposition solution includes at least one of a polypyrrole of about 0.1 M, about 1 mg/ml of graphite oxide gel, about 0.1 M of sodium p-toluenesulfonate, and about 0.25-1.0 mM of Iron (III) chloride.
  • the electric field results from a direct current voltage applied between the counter electrode and the working electrode for about 2 hours.
  • the catalyst-assisted polypyrrole/graphene nanocomposite film is prepared by a method which includes the steps of providing a graphite source and oxidizing the graphite source to form graphite oxide solution, washing the graphite oxide solution for thickening the graphite oxide solution, creating a dispersion of the graphite oxide solution in a liquid, thickening the graphite oxide solution to form a graphite oxide gel, introducing at least one reagent into an one-compartment cell, providing a deposition solution and dipping it in the graphite oxide gel, stirring the deposition solution for a particular time period, reacting the at least one reagent to form polypyrrole within the deposition solution, providing a substrate, and applying an electric field across at least a portion of the deposition solution dipped in the graphite oxide gel for depositing at least one portion of graphene from the graphite oxide gel and the deposition solution on the substrate to form polypyrrole and graphene nanocompo
  • Morphology of polypyrrole/graphene nanocomposite resulted from such techniques maximize the pseudocapacitive contribution of redox-active polypyrrole and electrical double layer capacitance (EDLC) contribution from individual graphene sheets.
  • EDLC electrical double layer capacitance
  • FIG.1 is an illustration of FESEM images of the surface of (a) C-PPy, (b) PPy, (c) 1.0 mM Fe C-PPy/GR, (d) Cross sectional view of 1.0 mM Fe C-PPy/GR, (e) High magnification of (d), and (f) HRTEM image of 1.0 mM Fe C-PPy/GR, according to an embodiment of the present invention.
  • the C-PPy film shows densely generated dendrite structure 105 of the present invention.
  • the PPy film grown in the absence of FeC by the same process has typical cauliflower morphology 1 10.
  • the PPy rods are possibly formed through micelle guided growth process, a phenomenon that has been observed with amphiphilic dopants, such as ⁇ -napthalenesulfonic acid, pyrenesulfonic acid and p-toluenesulfonic acid.
  • the own surfactant characteristic of pTS ions form micelles in the electrolyte solution where the hydrophobic pyrrole monomer is dissolved in micelles cluster.
  • the addition of oxidizing catalyst will polymerise the pyrrole monomer around the pTS micelle cluster that fuction as "template like" in forming the C-PPy rod.
  • those rods formed in the deposition solution electropolymerise onto the ITO glass.
  • the chemical polymers nano-PPy adheres onto the GO before the growth into rod-like PPy through micelles. After that, during electropolymerisation, the nano-PPy/GO sheets adheres to one another randomly and at the same time GO would be reduced to GR to form the C- PPy/GR composite.
  • Fig.1 illustrates top view of the catalyst-assisted electrochemical deposition of C- PPy/GR nanocomposite film with the addition of 1.0 mM FeCI 3 and the image reveals an extended porous and open structure 115 of the C-PPy/GR film.
  • a cross sectional view 120 of the nanocomposite film depicts a highly porous, 3 D structure formed from the random overlapping of GR sheets.
  • a magnified image of a single GR sheet shows that the PPy nano-particles 125 assembly homogeneously on the GR sheet.
  • PPy nanoparticles assemblies on GR sheet separate the neighboring GR sheets, accountable in forming sheets that bind to one another, resulting in a highly porous structure.
  • porous and 3D structure is most effective in facilitating penetration of electrolyte and increase the pseudocapacitive contribution of nano-PPy.
  • HRTEM was used to visualize the structure of 1.0 mM Fe C-PPy/GR.
  • Fig.l F illustrates black aggregates for PPy 130 has been homogeneously coated on GR sheets. The particle sizes of PPy are well controlled with diameter between 5-10 nm.
  • Fig. 2A illustrates the deposition process in the absence of a catalyst.
  • the pyrrole monomers within the vicinity of the electrodeposition area are electropolymerized and precipitated as PPy particles on the ITO as well as the adjacent GO sheets.
  • the electrodeposition process continue to take place on the surface of the film made up of the PPy particles instead. This is because the formation of a layer of film acts as a barrier that prevents the diffusion of additional pyrrole monomers into the intercalating spaces between the GR sheets, leading to the thick coating of PPy on the GR sheets.
  • polymeric aggregation worsens by the likelihood for electropolymerization to continue on any given polymer chain rather than nucleation of a new chain, which tend to enlarge present polymer particle.
  • the free electrons released from the formation of PPy would reduce GO to GR during the electrochemical deposition process. This result in large and continuous PPy particles coated on the GR surface but with little penetration into the inner layer of GR sheets, leading to the formation of dense, flat surface and blocking the electrolyte channel.
  • Such morphology reduces the contribution of pseudo capacitance from PPy and EDLC from GR since only surface of the film take part in the charge storage process.
  • FIG.2B is a schematic diagram illustrating a whole catalyst-assisted electropolymerization process, according to an embodiment of the present invention.
  • a catalyst-assisted deposition a low concentration of Fe 3+ is added into the solution.
  • Fe 3+ -catalyzed polymerization may also occur in addition to electropolymerization.
  • the Fe 3+ catalyst oxidize the pyrrole monomers to form PPy nanoparticles that decorate the individual GO sheets, simultaneously reducing Fe 3+ to Fe 2+ .
  • the subsequent electrodeposition process will unite the nano-PPy/GO sheets to one another and reduce the GO to GR, forming the scaffold of the C-PPy/GR composite.
  • the addition of the catalyst results in uniform deposition of nano-PPy throughout the graphene film. Subsequently, maximize the expose surface area of PPy and prevent the GR sheets restack by interrupting the forming of ⁇ - ⁇ interaction between neighboring GR sheets. Fe 3+ is regenerated simultaneously with the electrochemical oxidation of PPy nanoparticles and can be used again to synthesize PPy nanoparticles.
  • FESEM is used to characterize C-PPy/GR nanocomposite films prepared using various catalyst concentrations added into the deposition solution. Regardless of the catalyst concentration, the C-PPy/GR nanocomposites have a 3-D porous structure. However, the formation of nano-size PPy particles is dependent upon the amount of the catalyst added. In general, as the amount of the catalyst is increased, the extent of nanostructuring of PPy on GR surface also increased. Fig.
  • FIG. 3A depicts the top view of PPy/GR prepared in the absence of FeCI 3 , which has a dense, flat surface, which is made up of an alignment of GR and PPy through the ⁇ -electrons interaction.
  • Fig. 3B depicts the cross sectional view of the film, which consist of few layers made up of GR and PPy, agglomerated densely together.
  • a waxy but porous surface is yielded as illustrated in Fig.3C, and its cross sectional view shows reduced polymeric agglomeration as illustrated in Fig.3D, much unlike that is prepared without the catalyst.
  • Fig.3F illustrates a cross sectional view resembling that of the film grown electrochemical ly with 1.0 mM FeCI 3 .
  • the FESEM images of C-PPy/GR shows that the morphology can be controlled with combined polymerization processes (chemical polymerization and electropolymerization). Polymeric aggregation can be efficiently suppressed, forming nano-PPy particles homogeneously on GR when 1.0 mM of FeCI 3 catalyst is added into the deposition solution.
  • the changes of morphology are mainly due to the concentration of catalyst added into the deposition solution. Without the presence of catalyst in the deposition solution, the resulted morphology comprises dense layer with flat surface morphology. However, when 0.25 mM FeCI 3 is added, the polymeric agglomeration is reduced and the surface becomes more porous.
  • Nanostructured PPy is formed on the GR sheets when FeC is increased to 1.0 mM. Polymeric aggregation is completely inhibited, resulting in the decoration of nano-PPy on the GR surface that act as spacer where restacking of GR is successfully prevented.
  • FIG.4A is a graphical illustration of wide scans of GO, C-PPy, and C-PPy/GR nanocomposite film
  • FIG. 4B is a graphical illustration of de-convoluted XPS spectra of GO, C-PPy, and C-PPy/GR nanocomposite film, according to an embodiment of the present invention.
  • X-ray photoelectron spectroscopy XPS
  • Fig. 4A illustrate the wide scan
  • Fig. 4B illustrate de-convoluted C is XPS spectra of GO, C-PPy and C-PPy/GR.
  • the peak at 399.6 eV in the full XPS spectrum of C-PPy/GR indicates the presence of nitrogen from the PPy on the GR.
  • the XPS spectrum of the pure PPy film demonstrated four component peaks, which are observed at 283.9 eV, 284.4 eV, 284.9 eV and 286.3 eV, suggesting the presence of sp 2 hybridized carbon, sp 3 hybridized carbon, C-N groups and the C-S group from NapTS as a dopant.
  • the oxygenated carbons are detected in the XPS spectrum of C-PPy/GR, but the intensities of these peaks have far diminished from those in GO. The results indicate the deoxygenation of graphene oxide is during the electrodeposition process.
  • the obtained nanocomposites were further confirmed by XRD, as illustrated in Fig. 5.
  • the value of interplanar spacing depends the oxygen functionality on the surface of GO.
  • the high angle peak arises from PPy chain that is close to the inter-planar Van de Waals distance for aromatic groups and the peak at 16° corresponds to pyrrole counter ion, or intercounter ion interactions scattering.
  • the PPy/GR and C-PPy/GR nancomposites it presents crystalline peaks similar to that of PPy film, which ascribed to the diffraction peak of PPy.
  • the rod like structure may be less orderly compared with the typical cauliflower structure of PPy.
  • the Raman spectra obtained for GO, C-PPy and C-PPy/GR are shown in Fig. 6.
  • band located at 935, 981 , and 1052 cm "1 can be assigned to C-H out-of-plane deformation, ring deformation and C-H in plane deformation, respectively.
  • the G band corresponds to the vibration of sp 2 hybridized carbon while the D band indicates the defect or edge plane in the structure. Therefore, the D/G intensity ratio (I D :IG) expresses the atomic ratio of sp 2 /sp 3 carbons, to measure the extent of disordered graphite.
  • the calculated ID:IG ratio for GO is 0.89, which indicates extensive oxidation of GO in the process of chemical oxidation of graphite, leading to a reduction in the size of the in-plane sp 2 domains.
  • the : IG ratio (0.76) of C-PPy/GR significantly decrease after reduction, indicating the conversion of GO into GR.
  • the relatively large sp 2 domains of nanocomposite film indicating increase ⁇ - electron conjugation within the sp 2 domain.
  • the spectrum of nanocomposite shows a red-shift in the G band (1582 cm “1 ) as compared to GO (1600 cm "1 ), another evidence that the reduction of GO indeed takes place.
  • FT-IR Fourier-transform
  • the absorption bands related to oxygen containing groups on GO diminished, proving that GO entrapped in the PPy matrix had been effectively reduced.
  • the peaks at 1514, 1430, 1119 and 1003 cm '1 correspond to N-H bend, aromatic ring stretching, C-N stretching and N-H out-of-plane bending of PPy, showing the presence of PPy in the nanocomposite film.
  • CV is well known as an effective tool to investigate the capacitive behavior of a material. If the material is an ideal capacitor, it will exhibit several characteristics; high current, rectangular form of the voltammogram and symmetry in anodic and cathodic directions.
  • the cyclic voltammetry was carried out using a three-electrode one-compartment cell with 1 M of Na2S0 4 as the electrolyte. The potential was scanned from -0.2 to 0.8 V (versus Ag/AgCI) and the scan rate is varied from 2 to 100 mV/s.
  • CV curve recorded for PPy, PPy/GR and C-PPy/GR electrode is illustrated in Fig. 8A.
  • C-PPy/GR nanocomposite electrode exhibits high output current in comparison to the electrode of PPy and PPy/GR prepared under identical conditions without the presence of a catalyst, indicate enhancement of charge storage in C-PPy/GR.
  • Equation (1) Applying equation (1) to the CV curves for all of the electrodes yields specific capacitances ranging from 797.6 F/g for the 1.0 mM Fe C-PPy/GR, 689.6 F/g for the 0.5 mM Fe C-PPy/GR and 422.9 F/g for the 0.25 mM Fe C-PPy/GR electrodes to 296.9 F/g for the PPy/GR electrode and 157.4 F/g for PPy and 188.5 F/g for C-PPy.
  • 1.0 mM Fe C-PPy/GR has a higher particle density while still maintaining a relatively low average particle size, leading to a large redox-active surface area able to contribute to the material's pseudocapacitance, at the same time, does not hinder the EDLC performance of GR as the polymeric aggregation is prevented.
  • the contribution of pseudocapacitance from PPy and EDLC from GR are fully harnessed and exhibit superior charge storage performance in supercapacitor application.
  • the large and densely pack PPy particle growth of PPy/GR are undesirable for fast ion kinetics and is attributed to the decreased charge storage performance.
  • the CV curves of LOmM Fe C-PPy/GR with various scan rates are illustrated in Fig.8B.
  • the current density is increased with increasing scan rates, but does not indicate a greater charge capacitance at high scan rate. This can be attributed to the greater charge mobilization per unit time, where the increase of scan rate will lead to reduced of effective interaction between the ions and the electrode and the deviation from rectangularity of the CV become obvious at a scan rate of 50 and 100 mV/s.
  • Galvanostatic charge/discharge as illustrated in Fig. 9 are obtained at the current density of 1 A/g between -0.2 and 0.8 V versus Ag/AgCI in 1 M NaS0 4 for PPy, C-PPy, PPy/GR and 1.0 mM Fe C-PPy/GR.
  • Near-ideal EDLC behavior of the charge/discharge curves is seen by the symmetry of the charge and discharge slopes, where a triangle curve is observed. All of the curves illustrated in Fig. 9 are not ideal straight lines, indicating the involvement of a Faradaic reaction process of the PPy.
  • Electrochemical impedance spectroscopy is performed to investigate the mechanistic aspect for different nanostructures of PPy/GR electrode.
  • the EIS data were analyzed using Nyquist plot; a plot of the imaginary component (Z") of the impedance against the real component ( ⁇ ').
  • Nyquist plots of nanocomposites in the frequency range 100 KHz to 10 mHz are shown in Fig. 10.
  • a typical Nyquist plot of an ideal capacitor shows a small semicircle at high-medium frequency presented in the lower left portion of the spectra followed by a straight line in the low frequency region. All EIS plots in Fig.
  • FIG. 10 are shown to exhibit a straight line at low frequencies, indicating a pure capacitive behavior, representative of the ion diffusion in the electrode structure.
  • FIG. 10 shows magnified high frequency region of nanocomposite.
  • the impedance curves of PPy/GR and 1.0 mM Fe C-PPy/GR show a distorted and unobvious semicircle in the high-medium frequency region is attributable to good electronic conductivity of PPy/GR nanocomposite films.
  • the first intercept point of the semi-circle on the real axis represents equivalent series resistance (ESR). This corresponds to the total resistance due to resistance from the electrolyte, internal resistance of electrode and the contacts between the electrode and the current collector.
  • ESR equivalent series resistance
  • the diameter of the semicircle at medium frequency is associated with the double layer capacitance and charge transfer resistance (Ret).
  • the Ret is a resistance due to different conductivity in the nanocomposite (electronic conductivity) and the aqueous electrolyte phase (ionic conductivity). So the resistance arises due to discontinuities in the charge transfer process at the electrode/electrolyte interface. This forms an activation barrier (also called kinetic regime) that limits the migration of charge-complexes.
  • Open structures of GR sheets provide easier access (less resistance) for the intercalation and de-intercalation of charges compare with a flat and dense layer of GR in PPy/GR leading to low ESR of 1.0 mM Fe C-PPy/GR nanocomposite.
  • the charge transfer resistance for the 1.0 mM Fe C-PPy/GR is much lower than that of PPy/GR electrodes, indicating more efficient charge transfer kinetics compared to PPy/GR.
  • Fig. 11 shows the cycling performances of the two nanocomposites at 1 A/g by galvanostatic charge/discharge test.
  • the specific capacitance of 1.0 mM Fe C-PPy/GR decreases by ⁇ 25 % while that of PPy/GR decreases by -11 % after 1000 cycles.
  • GR sheets acted as interconnectors for improving the internal electrical conductivity and enhancing the specific surface area of the electrodes for EDLC charge storage.
  • the PPy acted as frameworks to bridge the GR sheets and prevent GR sheets from severe swelling and shrinking during the cycling process.
  • reducing particle size of PPy in 1.0 mM Fe C-PPy/GR exhibits impressive charge storage performance, however, the frameworks of nanocomposite are weakened due to disappearing of thick PPy coating and it may undergo serious structural alteration during the charge/discharge process leading to fast decrease of specific capacity retention.
  • Graphite powder is obtained from Ashbury Graphite Mills Inc., code no. 3061.
  • Sulphuric acid H 2 S0 , 95-98%
  • phosphoric acid H 3 P0 4 , 85%
  • potassium permanganate KMn0 4 , 99.9%
  • hydrogen peroxide H 2 0 2 , 30%
  • Hydrogen chloride HCI, 37%)
  • iron (III) chloride FeCI 3 , 98%) is purchased from Sigma-Aldrich.
  • Pyrrole (99%, Acros organic) is stored at 0 °C and distilled prior to use.
  • Sodium p-toluenesulfonate NapTS, 70 %) is purchased from Fluka.
  • GO is synthesized using the simplified Hummer's method.
  • Graphite oxide is obtained by oxidation of 3 g of graphite flakes with H2SO 4 :H 3 PO 4 (360:40 ml) and 18 g of KMnO 4 .
  • the mixing process is performed using a magnetic stirrer. The mixing process is completed in about 5 minutes. However, to ensure complete oxidation of graphite, the mixture was stirred for about 3 days. During the oxidation, the colour of the mixture changed from dark purplish green to dark brown. Subsequently, H 2 0 2 solution is added to stop the oxidation process, and the colour of the mixture changed to bright yellow, indicating a high oxidation level of the graphite.
  • the method for preparing graphene-based conducting nano-composite film further includes the step of creating a dispersion of the graphite oxide solution in the liquid and thickening the graphite oxide solution to form the graphite oxide gel includes exfoliating the graphite oxide in the liquid by repeatedly washing with de-ionized water and step of terminating oxidation of the graphite oxide solution is performed by adding hydrogen peroxide.
  • the graphite oxide formed is washed with 1 M of HCI aqueous solution and repeatedly with de-ionized water until a pH of 4-5 is achieved.
  • the washing process is carried out using a simple decantation of the supernatant using the centrifugation technique.
  • the graphite oxide experienced exfoliation, which resulted in the thickening of the GO solution. Consequently, the thickening of the GO solution resulted in the formation of the GO gel.
  • the concentration of the GO gel is about 4.38 mg/ml.
  • the step of applying the electric field includes providing an electrophoresis solution includes a supporting electrolyte, and forming the graphene-based conducting nanocomposite film on a surface of the substrate.
  • the nanocomposite film is formed on the surface of the substrate by simultaneously depositing the at least one portion of the deposition solution and the at least one portion of graphene from the graphite oxide gel onto the surface of the substrate by an electrophoresis deposition (EPD) method in a proper electrophoresis deposition (EPD) condition.
  • EPD electrophoresis deposition
  • the step of forming of the nanocomposite film includes electro-chemical processing and the time period is about 30 minutes to allow polypyrrole to form in the deposition solution.
  • PPy/GR nanocomposite films are synthesized by catalyst-assisted electrochemical polymerization from an aqueous solution placed in a one-compartment cell.
  • the deposition solution contained 0.1 M pyrrole, 1mg/ml GO, 0.1 M NapTS and 0.25-1.0 mM FeCl3, and the solution is vigorously stirred for 30 minutes to allow PPy to form in the solution.
  • the concentration of FeC is kept low to ensure that the polymer is doped primarily with pTS " ions.
  • the solution is then transferred to deposition cell, and PPy/GR is deposited at a constant potential of +0.8 V using potentiostat-galvanostat (Elchema model EQCN-502 Faraday cage) at room temperature.
  • the graphite electrode is used as the counter electrode and indium tin oxide (ITO) is used as the working electrode.
  • ITO indium tin oxide
  • a saturated calomel electrode (SCE) is used as reference electrode and all the potentials are referred to the saturated calomel electrode (SCE).
  • the time of polymerization is about 2 hours.
  • a 0.1 M PPy/GR nanocomposite film without catalyst is synthesized and 0.1 M PPy film is synthesized with and without catalyst.
  • the surface morphology of GO, PPy, C-PPy, PPy/GR and C-PPy/GR is investigated using field emission scanning electron microscopy (FESEM, FEI Nova NanoSEM 400).
  • FESEM field emission scanning electron microscopy
  • HRTEM High resolution transmission electron microscopy
  • XRD Siemens D5000 X-ray diffraction
  • Raman spectra is measured using a Renashaw's inVia Raman microscope with a 532 nm laser and FT-IR spectra are recorded on a Perkin-Elmer model 1725x.
  • the electrochemical properties of the materials are measured using the VersaSTAT 3 electrochemical system (Princeton Applied Research). Cyclic voltametry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS) are all carried out in a three-electrode cell system, including nanocomposite films as the working electrode, platinum wire as a counter electrode and Ag/AgCI as the reference electrode, is employed to conduct the experiment. CV was carried out at between -0.2 and 0.8 V (versus Ag/AgCI) at scan rates between 2 and 100 mV/s. The specific capacitance values of the samples are calculated from cyclic voltammograms using Equation (1).
  • Cm i s Equation (1)
  • Cm is the specific capacitance in farads per gram
  • J * is the integrated area of the CV curve
  • m is the mass of the electrode material in grams
  • 5 is the scan rate in volts per second.
  • Galvanostatic charge/discharge are carried out between -0.2 and 0.8 V (versus Ag/AgCI) at a current density of 1 A/g and the long term cycling performance of the PPy/GR and 1.0 mM Fe C-PPy/GR electrodes are measured by the consecutive galvanostatic charge-discharge at a current density of 1 A / g for 1000 cycles.
  • An EIS is carried out between 100 KHz to 10 mHz with an ac amplitude of 5mV.
  • the present invention provides a simple method for preparing polypyrrole and graphene nanocomposite films using a catalyst-assisted electrochemical deposition method with significantly enhance charge storage performance.
  • the present invention evidently illustrates that by FESEM that the particle size of PPy is able to be controlled using different catalyst amount and nano-sized PPy is formed with 1.0 mM of FeCI3 as a catalyst.
  • PPy in nano-sized dimension that could not be formed as elongation instead of nucleation of PPy occurred. This explains the formation of a thick layer PPy in the nanocomposite in the absence of the catalyst.
  • the PPy decorated graphene enabled the efficient transfer of electrons as well as ions within the matrix of the nanocomposite.
  • the specific capacitance of as obtained C-PPy/GR is high as 797.6 F/g and the impressive performance of C-PPy/GR is attributed to the unique morphology of C-PPy/GR allowed the pseudo capacitance of PPy and EDLC of GR to be fully harnessed.
  • the present invention provides one or advantages stated above and the catalyst-assisted electrochemically synthesize C- PPy/GR nanocomposite is a promising candidate for high performance supercapacitors. It is to be understood that the above description is intended to be illustrative, and not restrictive.

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Abstract

La présente invention concerne un procédé de préparation de films nanocomposites à base de polypyrrole et de graphène comprenant les étapes consistant à laver une solution d'oxyde de graphite afin de l'épaissir, à générer une dispersion dans un liquide de la solution d'oxyde de graphite, à épaissir la solution d'oxyde de graphite afin d'obtenir un gel d'oxyde de graphite, à introduire au moins un réactif dans une cuve à un seul compartiment, à utiliser une solution de dépôt et à la placer dans le gel d'oxyde de graphite, à agiter ladite solution de dépôt pendant un laps de temps bien défini, à faire réagir le ou les réactifs afin d'obtenir du polypyrrole au sein de la solution de dépôt, à utiliser un substrat et à appliquer un champ électrique à travers au moins une partie de la solution de dépôt placée dans le gel d'oxyde de graphite afin d'entraîner le dépôt d'au moins une partie du graphène en provenance du gel d'oxyde de graphite et de la solution de dépôt sur le substrat afin d'obtenir des films nanocomposites à base de polypyrrole et de graphène.
PCT/MY2014/000054 2013-07-30 2014-04-11 Procédé de préparation assistée par catalyseur d'un film de graphène décoré de nanoparticules de polypyrrole pour supercondensateur haute performance WO2015016700A1 (fr)

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CN115172066A (zh) * 2022-06-16 2022-10-11 宁德师范学院 一种Fe3+诱导的褶皱石墨烯基电容复合材料及其制备方法

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CN106270497A (zh) * 2016-08-10 2017-01-04 安徽省宁国天成电工有限公司 一种高导热合金‑石墨烯复合材料的制备方法
CN106270497B (zh) * 2016-08-10 2018-06-26 安徽省宁国天成电工有限公司 一种高导热合金-石墨烯复合材料的制备方法
CN109950052A (zh) * 2019-03-22 2019-06-28 北京石油化工学院 一种超级电容器的制备方法
CN111999364A (zh) * 2020-08-27 2020-11-27 合肥海关技术中心 一种用于沙门氏菌检测的dna电化学传感器及其制备方法
CN113241261A (zh) * 2021-05-11 2021-08-10 合肥师范学院 一种层叠交联结构超级电容器电极材料、其制备方法及其应用
CN113611875A (zh) * 2021-08-05 2021-11-05 中汽创智科技有限公司 一种复合催化剂及其制备方法和应用
CN113511651A (zh) * 2021-09-09 2021-10-19 成都特隆美储能技术有限公司 一种聚吡咯修饰微氧化膨胀石墨负极材料的制备方法
CN113511651B (zh) * 2021-09-09 2021-11-26 成都特隆美储能技术有限公司 一种聚吡咯修饰微氧化膨胀石墨负极材料的制备方法
CN115172066A (zh) * 2022-06-16 2022-10-11 宁德师范学院 一种Fe3+诱导的褶皱石墨烯基电容复合材料及其制备方法
CN115172066B (zh) * 2022-06-16 2023-04-25 宁德师范学院 一种Fe3+诱导的褶皱石墨烯基电容复合材料及其制备方法

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