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WO2012064292A1 - Procédé de préparation de composites au graphène sans polymère/oxygène utilisant un processus électrochimique - Google Patents

Procédé de préparation de composites au graphène sans polymère/oxygène utilisant un processus électrochimique Download PDF

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Publication number
WO2012064292A1
WO2012064292A1 PCT/TH2011/000036 TH2011000036W WO2012064292A1 WO 2012064292 A1 WO2012064292 A1 WO 2012064292A1 TH 2011000036 W TH2011000036 W TH 2011000036W WO 2012064292 A1 WO2012064292 A1 WO 2012064292A1
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Prior art keywords
graphene
pedot
solution
pss
polymer
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Ceased
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PCT/TH2011/000036
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English (en)
Inventor
Adisorn Tuantranont
Chakrit Sriprachabwong
Anurat Wisitsoraat
Ditsayut Phokharatkul
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National Science and Technology Development Agency
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National Science and Technology Development Agency
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Priority claimed from TH1001001731A external-priority patent/TH1001001731A/th
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Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink

Definitions

  • the present invention relates to the field of nanocomposite materials and particularly concerns with the preparation of polymer-graphene composites by electrochemical processes.
  • the composite obtained through said method can readily be used to deposit electrically conductive layers on a given substrate by inkjet printing mean for a variety of applications including transparent conductors, transparent antenna, electrochemical electrodes and so on.
  • Nanotechnology is the science concerned with an invention that is very small in the nanometer or molecular scale. Nanotechnology can be classified into three major fields including nanomaterials, nanoelectronics and nanobiotechnology. Among these, nanomaterials, which concern the creation of nanostructured materials, is considered as the most important basis that support other aspects of nanotechnology. There are a wide range of nanostructured materials including nanopowders, nanotubes, nanofibre nanorod, nanowires, nanoplates, etc. These materials are very useful in the field of gas/chemical/biosensor technology because their high specific surface area can enable ultra sensitive detection at molecular or atomic level.
  • Graphene is the latest nanocarbon material with a two dimensional (2D) honeycomb hexagonal structure of sp 2 covalently bonded carbon atoms. Its unique atomic configuration leads to various astonishing properties including a very large surface area of 2630 m /g (double of single-walled carbon nanotubes (SWCNTs)), very high electrical/thermal conductivity, a tunable band gap, room-temperature Hall effect, high mechanical strength (200 times greater than steel) and high elasticity.
  • SWCNTs double of single-walled carbon nanotubes
  • graphene has been widely studied for various electronic applications such as transistors, memory device, photovoltaic (solar cell), gas/chemical/biosensors, etc.
  • graphene has several advantages over CNTs due to two major issues. Unlike CNTs, graphene can be produced with no metallic impurities that are undesirable in many applications such as electrochemical sensing. Secondly, graphene can be manufactured from low-cost graphite.
  • Graphene can generally be synthesized by several methods including micromechanical cleavage, epitaxial growth via ultra-high vacuum graphitation, chemical synthesis through oxidation of graphite, chemical vapor deposition (CVD), solvothermal synthesis, and other innovative methods, for example “wet ball graphite milling in polymer and organic solvent” [Ref. 1], which has advantages of high graphene production yield and throughput but suffers from complexity and impurities from ball milling.
  • graphene is produced by means of "ultrasonic dispersion, liquid-solid graphite separation".
  • graphene is produced by applying a dc voltage to graphite rods immersed in polystyrene solution, causing oxidation reaction to exfoliate graphene from graphite.
  • the electrolytic exfoliation method offers many advantages including ability to produce stable graphene in solution, capability to form single-layer graphene, ease of large scale production and low cost.
  • graphene has been widely applied in conjunction with polymers in order to improve their mechanical and electrical properties.
  • Graphene has been blended with various types of polymers such as epoxy, polystyrene (PS), polyaniline (PANI), polyurethane (PU), polyvinyldene fluoride (PVDF), Nafion, polycarbonate, polyethylene terephthalate (PET), polyvinyl alcohol (PVA), poly 3,4-ethyldioxythiophene (PEDOT), etc in order to improve their mechanical strength.
  • PS polystyrene
  • PANI polyaniline
  • PU polyurethane
  • PVDF polyvinyldene fluoride
  • Nafion polycarbonate
  • PET polyethylene terephthalate
  • PVA polyvinyl alcohol
  • PEDOT poly 3,4-ethyldioxythiophene
  • graphene has been mixed with conductive polymer such as PANI and PEDOT to enhance their electrical conductivity.
  • graphene-PEDOT composite in thin-film form offers superior transparency, conductivity, flexibility as well as temperature stability suitable for a variety of applications [Ref. 13].
  • highly conductive graphene film has been coated on various polymer films for electronic packaging [Ref. 14-15].
  • polymer-graphene mixing process usually requires multi-step chemical-reaction processes, which are complicated and not cost effective. Therefore, simpler polymer-graphene preparation processes are highly needed for practical applications.
  • Polymer-graphene composite which are normally prepared in solution form, can be used by several means such as spin-coating, spray coating and inkjet printing.
  • Inkjet printing technology is well-known for two-dimensional image creation in Art work or printed documents.
  • plastic microelectronic circuit fabrication with much lower cost and simpler manufacturing process than standard photolithographic technology.
  • graphic design software to draw the layout and print several layers to obtain the desired circuit with a. high resolution of 5-10 microns.
  • it uses non-contact patterning and low temperature process so that a wide variety of substrates can be used. It is thus a promising platform for various industrial applications such as low cost and disposable sensors, etc.
  • biosensors, gas sensors and several types of transducers fabricated by inkjet printing have been demonstrated.
  • a high performance transistor-type biosensor has been developed by inkjet printing of a polymer- graphene active layer [Ref. 16].
  • the invention provides preparation method of polymer-graphene composite by an electrochemical process and presents characteristics of prepared polymer-graphene composite as a function of process parameters such as applied voltage.
  • process parameters such as applied voltage.
  • physical and electrical characteristics examined by transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman Spectroscopy, Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), 4-point probe measurement and cyclic voltametry are reported.
  • TEM transmission electron microscopy
  • AFM atomic force microscopy
  • FTIR Fourier transform infrared spectroscopy
  • DLS dynamic light scattering
  • 4-point probe measurement and cyclic voltametry 4-point probe measurement and cyclic voltametry.
  • the unique property of produced graphene is oxygen-free while the polymer-graphene composites are demonstrated to be highly transparent and conductive.
  • the invention also includes the use of polymer-graphene composite produced by the said method as an ink for inkjet printing to deposit electrically conductive layers on a given substrate for a variety of applications including transparent conductors, transparent antenna, electrochemical electrodes, and so on.
  • Fig. 1 shows a drawing of apparatus for preparation of polymer-graphene composite by electrochemical method.
  • Fig. 2 is an Atomic force microscopic (AFM) images of graphene-PEDOT:PSS layers coated on a silicon substrate.
  • AFM Atomic force microscopic
  • Fig. 3 is a typical transmission electron microscopic images of graphene synthesized in the PEDOT:PSS polymer matrix.
  • Fig. 4 is a typical select area electron diffraction (SAED) pattern of synthesized graphene sheets.
  • Fig. 5 shows a typical Raman spectrum of graphene synthesized in the PEDOT:PSS polymer matrix.
  • Fig. 6 shows a typical FTIR spectra of PEDOT/PSS, graphene-PEDOT/PSS and washed graphene-PEDOT/PSS. Synthesized voltage and time are 8 Vand 40 hours, respectively.
  • Fig. 7 is a Graph showing the effect of voltage on the particle size of graphene dispersed in the PEDOT:PSS solution measured by dynamic light scattering.
  • Fig. 8 is a graph Conductivity vs. Voltage of graphene-PEDOT/PSS thin films synthesized at different electrolytic times.
  • Fig. 9 Optical transmittance spectra in UV/VIS region (300-800 nm) of spin-coated PEDOT/PSS and graphene-PEDOT/PSS thin films synthesized at various electrolytic voltages for 40 hours. Inset is transmittance at 550 nm vs. voltage.
  • Fig. 10 Photograph of (a) inkjet printed graphene-PEDOT/PSS film and (b) RFID antenna on transparencies.
  • Fig. 11 Photograph of fabricated electrode and SEM micrographs of SPCE, inkjet-printed PEDOT:PSS on SPCE and printed graphene-PEDOT:PSS on SPCE.
  • Fig. 12 Cyclic voltammogram of 1 mM salbutamol on (a) graphene-PEDOT:PSS and (b) PEDOT electrode and (c) SPCE electrode. Scan rate was lOOmVs -1 . Buffer solution was 50 mM phosphate buffer (pH 7.0).
  • Graphite rod is used as starting material for graphene synthesis.
  • Two graphite rods are placed in an electrolysis cell filled with an electrolyte and a constant potential in the range of 3-12 V is applied between them using a regulated dc power supply for 4-10 hours.
  • the electrolyte is the solution of conductive polymer, e.g.
  • FIG. 2 The typical topography of graphene dispersed in PEDOT:PSS polymer characterized by atomic force microscopy (AFM) is illustrated in Fig. 2.
  • AFM sample is prepared by dropping the graphene - PEDOT/PSS solution onto a silicon substrate and drying overnight at room temperature before AFM measurement. From the 2x2 micron AFM image, several graphene sheets with nanometer-scale thickness are overlapping and the average height (thickness) of graphene sheets is estimated to be in the range of 0.7-1 nm.
  • TEM samples are prepared by dropping the solution onto the carbon/copper grid TEM and drying in a desiccator over night. It can be seen that it contains polygon sheets with unequal sides mixed and surrounded by very smooth material. In addition, polygon sheets are seen to have some thickness variation, suggesting more than one overlapping material layers. Their average diameter is estimated to be around 500 nm.
  • SAED selected area electron diffraction
  • Raman Spectroscopy is used to study the quality of graphene structure synthesized in PEDOT/PSS's matrix.
  • graphene powder is extracted from graphene- PEDOT/PSS solution by centrifugation at 10,000 rpm, washing in DI water and ethanol and drying in an oven temperature at 80 °C.
  • Raman spectrum from extracted graphene powder synthesized at electrolytic voltage of 8 V is shown in Fig. 5. It is evident that all spectra contain three peaks at -1330, -1580 and -2600 cm “1 , corresponding to D, G and 2D bands, respectively.
  • G band is considerably sharper and stronger than D and 2D bands.
  • G band is well- known to be associated to sp 2 honey comb graphitic carbon structure.
  • G band of SWCNTs is relatively broad because it contains two degenerate peaks (G+ and G-) while G band of graphene has only one sharp peak, which is evident in Fig. 5.
  • High quality graphene will have low D peak due to low edge defect density attainable from wide and thin graphene structures.
  • 2D band is contributed by zone- boundary defects and its shape can be used to differentiate graphene from graphite and suggest type of graphene.
  • Single-layer graphene has only a single sharp 2D peak and 2D band will be broaden and contain more than one components for multi-layer graphene and graphite. From Fig.5, 2D band is relatively broad compared to G band suggesting that all synthesized graphenes have multiple layers.
  • the functional groups of PEDOT/PSS, graphene-PEDOT/PSS and washed graphene powders are characterized by FTIR as illustrated in Fig. 6.
  • graphene does not contribute additional functional group to the mixture.
  • the produced graphene is oxygen-free. This property is uniquely derived from this preparation method and desirable for a variety of applications. It should be noted that the graphene-PEDOT/PSS was sysnthesized at 8V for 40 hours and FTIR results from graphene- PEDOT/PSS produced at other voltages are not shown because they are approximately the same.
  • Fig. 7 The effect of voltage on the graphene particle size in the dispersion measured by dynamic light scattering (DLS) is shown in Fig. 7. It can be seen that the particle size tends to increase as the applied voltage increases and there are particles with two different average sizes at high applied voltage of more than 3 V. At low voltage of 3 V, all graphene particles have the average size of 2016 nm. For the voltage of 5 V, 82.2. % and 17.2% of particles have the average sizes of 4159 and 326.2 nm, respectively. At higher voltage of 8 V, the two average particle sizes increase to 4738 and 226.3 nm and their concentrations are 90.2% and 9.8%, respectively.
  • Graphene-PEDOT/PSS thin film is deposited on transparencies by inkjet printing with varying electrolytic voltages and times.
  • the electrical conductivity and optical transmittance of deposited film are characterized for transparent electrode applications by four-point probe measurement and UV/VIS spectroscopy.
  • the conductivity of spin-coated graphene-PEDOT/PSS thin films prepared at different electrolytic voltages and times are shown in Fig. 8.
  • the conductivity is calculated from the sheet resistance measured by four point probe and the film thickness determined from stylus profiler.
  • the thickness of all inkjet printed films is found to be approximately 90 nm. It can be seen that the conductivity of graphene-PEDOT/PSS thin films monotonically increases with time and applied voltage.
  • the time dependence of conductivity is approximately linear with some statistical variation while its voltage dependence is nonlinear. At low voltage of 3 and 5 V, the conductivity is slowly increasing with voltage, then rapidly rising when the voltage increases to 8 V and going up slowly again as the voltage increases further.
  • the improved electrical conductivity can be attributed to graphene' s high 2D electrical conductivity, which is also depending on the quality of produced graphene structure.
  • the observed voltage dependence of conductivity implies that the quality of graphene is critically improved at the electrolytic voltage between 6 V and 8 V and further voltage increment only slightly enhances electrical conductivity.
  • the conductivity of optimized graphene-PEDOT/PSS film is more than 3 times higher than that of unloaded PEDOT/PSS film (-6.2 S/cm).
  • the optical transmittance spectra in UV/VIS region (300-800 nm) of inkjet printed PEDOT/PSS and graphene-PEDOT/PSS thin films synthesized at different voltages for 40 hours are shown in Fig. 9.
  • PEDOT/PSS thin film has high transmittance in visible region.
  • the transmittance spectra of PEDOT/PSS thin films are modified differently depending on electrolytic voltage.
  • the transmittance only slightly decreases by a fraction of percent in a short wavelength region between 350 and 550 nm while the transmittance remains approximately the same at higher wavelengths.
  • the transmittance monotonically decreases throughout the visible region when the electrolytic voltage increases to 5 V and 8 V and the reduction considerably increases as the electrolytic voltage increases.
  • the transmittance when the voltage increases to 12 V, the transmittance, however, only slightly decreases further and most reduction occurs in the short wavelength region.
  • the transmittance at the center of visible region (550 nm) is calculated and plotted as a function of electrolytic voltage as shown in the inset of Fig. 8. It is evident that the transmittance decreases by around 3% as the voltage increases from 3 to 8 V but then becomes much less voltage dependent when the voltage further increases to 12 V. Thus, the observed voltage dependence of transmittance indicates that the absorption due to graphene is critically increased at the electrolytic voltage of around 8 V and beyond.
  • FIG. 10 The photograph of typical inkjet printed transparent conducting film on transparencies is shown in Fig. 10. It can be seen that the inkjet printed graphene-PEDOT/PSS film is highly uniform and transparent such that the small logos are clearly visible (Fig. 10 (a)).
  • the transparent inkjet printed film is potential for a variety of applications including radio-frequency identification (RFID), flexible organic display and solar cell.
  • Fig. 10 (b) illustrates a transparent RFID antenna prepared by inkjet printing.
  • the transparent antenna is highly desirable for RFID tags on packages of consumer products because it is almost invisible so that it can be placed anywhere on a package without affecting label's visibility.
  • RFID antenna based on inkjet printed graphene- PEDOT/PSS film offers advantages including simple low-temperature fabrication process and low cost.
  • the polymer-graphene antenna contains no metallic impurities. Thus, it will not be falsely detected by security-checked x-ray scanner.
  • Inkjet printed polymer-graphene film can also be used as an electrochemical sensing layer on a suitable supporting electrodes or substrates including screen printed carbon electrodes (SPCEs), glassy carbon electrode, gold and platinum electrodes.
  • SPCEs screen printed carbon electrodes
  • electrochemical sensor based on inkjet-printed graphene-PEDOT/PSS SPCE has been fabricated over ah area of 3 mm x 5 mm. The electrochemical characteristics of the modified SPCEs are measured by cyclic voltammetry (CV) toward a model analyte, salbutamol, which is a prohibited drug in sport and a banned food additive.
  • CV cyclic voltammetry
  • Fig. 11 includes a photograph of fabricated electrodes and SEM micrographs of unmodified SPCE, inkjet-printed PEDOT/PSS SPCE and inkjet-printed graphene-PEDOT/PSS SPCE. It can be seen that uncoated SPCE has rough surface with large grains of several microns in size and the surface is smoothen after inkjet printing with PEDOT/PSS or graphene-PEDOT:PSS layers. However, graphene structures are not clearly observed on the SPCE surface because graphene sheet (-0.5 ⁇ in diameter) is very small compared to the surface roughness and grain of SPCE.
  • the oxidation peak amplitudes of PEDOT/PSS modified and graphene-PEDOT/PSS modified SPCEs are approximately 30 and 150 times higher than that of unmodified SPCE, respectively.
  • PEDOT/PSS considerably enhances the electrochemical activity of SPCE to salbutamol and the addition of graphene greatly increases the response further.
  • the dramatic enhancement can be attributed to huge reactive surface area, high electronic mobility and excellent electron transfer rate of graphene-PEDOT/PSS composite.

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Abstract

La présente invention concerne la préparation et l'utilisation de composites au graphène sans polymère/oxygène par un processus d'exfoliation électrolytique. Deux tiges de graphite sont placées dans une cellule d'électrolyse remplie d'un électrolyte et un potentiel constant compris entre 3 et 10 V est appliqué entre elles en utilisant une alimentation électrique en CC régulé pendant 4 à 10 heures et des précipités noirs de graphène se formeront dans la solution. L'électrolyte est la solution de polymère conducteur, par ex. polythiophène (PTh), poly-3,4-éthyldioxythiophène/acide polystyrènesulfonique (PEDOT/PSS), polyaniline (PANI), polypyrrole (PPy), polyphénylène vinylène (PPV), polyacétylène (PA), polythiénylène et leurs dérivés. Le produit précipité est alors centrifugé à une vitesse comprise entre 10 000 et 20 000 tr/min pour retirer les gros agglomérats en décantant la partie surnageant dans la dispersion. La solution dispersée est alors utilisée comme encre pour l'impression à jet d'encre.
PCT/TH2011/000036 2010-11-11 2011-08-25 Procédé de préparation de composites au graphène sans polymère/oxygène utilisant un processus électrochimique Ceased WO2012064292A1 (fr)

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Cited By (12)

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CN102815043A (zh) * 2012-08-02 2012-12-12 中国科学技术大学 一种石墨烯和聚苯胺复合纸的制备方法及其产品
CN104003377A (zh) * 2014-05-26 2014-08-27 上海大学 一种高比电容的还原氧化石墨烯的制备方法
CN104078742A (zh) * 2013-03-27 2014-10-01 上海德门电子科技有限公司 一种透明介质天线
US20140342142A1 (en) * 2013-05-20 2014-11-20 Enerage Inc. Graphene transparent conductive film
CN104264179A (zh) * 2014-09-17 2015-01-07 中国科学院山西煤炭化学研究所 一种由石墨原矿电解法制备石墨烯的方法
JP2016534002A (ja) * 2013-07-04 2016-11-04 フォンダツィオーネ インスティテゥート イタリアーノ ディ テクノロジア ポリアニリン／還元型酸化グラフェン複合体の調製法
CN106916489A (zh) * 2017-03-14 2017-07-04 江南大学 一种通过层层喷印制备的sps:pedot/rgo复合导电涂层
US10157338B2 (en) 2016-05-04 2018-12-18 International Business Machines Corporation Graphene-based micro-scale identification system
WO2019129573A2 (fr) 2017-12-29 2019-07-04 Sixonia Tech Gmbh Procédé de fabrication d'un matériau semi-conducteur ou conducteur fonctionnalisé et son utilisation
CN112830568A (zh) * 2021-01-07 2021-05-25 南开大学 一种电化学原位诱导聚苯胺负载石墨烯修饰电极的制备方法及应用、除镉方法
CN113466300A (zh) * 2021-07-16 2021-10-01 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法
CN116093359A (zh) * 2022-12-26 2023-05-09 湖北工业大学 一种氧化石墨烯复合材料及其制备方法和应用

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