WO2022093005A1 - A method for preparing a graphene-based conductive film - Google Patents

A method for preparing a graphene-based conductive film Download PDF

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WO2022093005A1
WO2022093005A1 PCT/MY2020/050198 MY2020050198W WO2022093005A1 WO 2022093005 A1 WO2022093005 A1 WO 2022093005A1 MY 2020050198 W MY2020050198 W MY 2020050198W WO 2022093005 A1 WO2022093005 A1 WO 2022093005A1
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graphene
colloid
conductive film
conductive polymer
functionalized
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French (fr)
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Nora'zah Binti ABDUL RASHID
Nur Diyana Syazwani Binti ZAMBRI
Aiman Sajidah Binti ABD AZIZ
Syed Muhammad Hafiz Bin SYED MOHD JAAFAR
Suraya Binti SULAIMAN
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Mimos Berhad
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity

Definitions

  • the present invention relates to preparation of graphene-based conductive film for flexible electronics, more particularly a method for preparing a reduced graphene oxide-silver nanoparticles conductive film through inkjet printing.
  • Flexible electronics is a technology that allows building of electronic circuits on flexible substrates thus making them foldable and stretchable.
  • the main advantages of flexible electronics are the low cost manufacturing through inkjet printing and inexpensive flexible substrate such as plastics, paper, textiles or metal foils. Therefore, flexible electronic has gained great attention due to its ability in providing cost effective solutions to wide area of applications such as rollable displays, electronic paper, flexible cellular phone, solar cells, RFID-tags, wearable sensors for health monitoring, lab-on-a-chip for disease diagnostics, flexible temperature sensors for healthcare and et cetera.
  • graphene with superior electrical and thermal conductivities has been widely used as a based material in production of conductive film.
  • the production process of graphene-based material such as chemical reduction is usually unable to remove all the oxygen in graphene oxide thereby creating defects and vacancies to produce graphene-based material with lower quality as compared to pristine graphene.
  • the graphene-based conductive film produced through inkjet printing is potentially causing several issues.
  • the film with lower hardness can cause film rupture and thus generate adhesion issue.
  • the methods to functionalize graphene-based material such as addition of conductive polymers into graphene-based material have been developed to reinforce the film hardness.
  • the existing methods also degrade the electrical performance of the film and lead to clogging issue in inkjet printing while increasing the film hardness. Accordingly, an improved method with simpler steps is required in order to effectively address the aforementioned issues.
  • US20160244577 A1 discloses a method for manufacturing a graphene polymer conductive film.
  • the method comprising the steps of providing a graphene powder and a plurality of conductive monomers; providing a solvent and producing a graphene dispersion liquid by stirring and ultrasonic processing after mixing the graphene powder into the solvent; producing a mixed liquid having the graphene and the conductive monomers by stirring and ultrasonic processing after mixing the conductive monomers into the graphene dispersion liquid; mixing an initiator into the mixed liquid of the graphene and the conductive monomers for in situ polymerization to produce a pre-liquid of a graphene conductive polymer composite material; producing a powder of the graphene conductive polymer composite material by removing solvent and impurity in the pre-liquid of the graphene conductive polymer composite material through a filtration and drying process; providing, mixing and stirring an epoxy resin, a curing agent and an accelerator until uniformly distributed to produce epoxy resin glue system; distributing the powder of the graph
  • CN103839608A discloses a method for preparing graphene conductive film.
  • the method comprising the steps of adding graphite or graphite derivative to the dispersant/ethanol/dimethyl formamide organic solvent to obtain dispersion liquid; subjecting the dispersion liquid to high density ultrasonication to obtain a monomolecular layer or a multilayer graphene solution, and the upper layer liquid is taken after high-speed centrifugation, and the graphene powder is obtained after flocculation treatment; dispersing the graphene powder into an organic solvent to prepare an inkjet ink; injecting the inkjet ink into the ink cartridge and deposited onto the pre-processed substrate in a predetermined pattern by conventional inkjet printing technology; drying the conductive film deposited on the substrate in an oven to obtain graphene conductive film.
  • Jiantong Li et al., Efficient Inkjet Printing of Graphene, Advanced Materials, Volume 25, 29 (2013), 1 -8 discloses a method for preparing graphene conductive film using inkjet printing.
  • the graphene is first exfoliated from graphite flakes in dimethylformamide which is DMF. After that, the low viscosity and toxic DMF is changed to high-viscosity and environmental-friendly terpineol through distillation to concentrating the graphene.
  • the graphene/terpineol dispersion Prior to printing, the graphene/terpineol dispersion is mixed with ethanol to optimize the viscosity and surface tension for inkjet printing.
  • the transparent conductive films are fabricated by printing the graphene inks onto untreated glass slides. After printing, the stabilizing polymers can be effectively removed through a simple annealing process.
  • the aforesaid methods for preparing graphene-based conductive films are complicated as several additional steps such as polymerization process and drying process are required. Indirectly, said additional steps increase the production cost. Additionally, the aforesaid methods involve the use of toxic chemicals that may cause harm to human and environment. It is apparent that the aforesaid prior arts are lacking a simple, cost effective and harmless method for preparing graphene-based conductive film with improved hardness without degrading its electrical performance.
  • the present invention provides a method for preparing a graphene-based conductive film.
  • the present invention discloses a method for preparing a graphenebased conductive film characterized by the steps of: adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid; adding dispersants into said functionalized colloid; vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid; and depositing said graphene-based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film.
  • Figure 1 shows a flow chart of a method (100) for preparing a graphenebased conductive film in accordance to an embodiment of the present invention
  • compositions or an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition, element or group of elements with transitional phrases “consisting of”, “consisting”, “selected from the group of consisting of, “including”, or “is” preceding the recitation of the composition, element or group of elements and vice versa.
  • a method (100) for preparing a graphene-based conductive film of the present invention encompasses adding of a conductive polymer to functionalize a graphene-based nanoparticles colloid to improve hardness without degrading the electrical performance of the film.
  • the method (100) for preparing graphene-based conductive film comprises the steps of adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid (104); adding dispersants into said functionalized colloid (110); vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid (112); and depositing said graphene- based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film (116).
  • the graphene-based nanoparticles colloid is reduced graphene oxide-silver nanoparticles colloid in a range of 0.08 g/mL to 0.12 g/mL.
  • the conductive polymer is selected from the group consisting of polypyrrole, polyanilene and its derivatives, polyindole, more preferably a doped polypyrrole in a range of 0.02% w/v to 0.15% w/v.
  • Doped polypyrrole is a cost efficient conducting polymer with high thermal and chemical stabilities as well as high solubility in water.
  • the step of adding conductive polymer (104) further comprises the steps of stirring the colloid mixture at 900 rpm to 1000 rpm at the temperature of 25°C to 30°C for 1 hour (106) after adding conductive polymer; and sonicating the colloid mixture at 55°C to 65°C for 1 hour to obtain said functionalized colloid (108).
  • the dispersants are selected from the group consisting of ethylene glycol, terpineol, methanol, ethanol, 2-propanol, cyclohexanone or combination thereof, more preferably a combination of ethylene glycol, terpineol and methanol.
  • Ethylene glycol is a polar solvent that interacts with oxygen functional group on the graphene-based surface to prevent functionalized colloid from aggregation and thus produce a uniform dispersion.
  • Terpineol is a natural oil for enhancing dispersion of functionalized colloid and thus helps in obtaining of a smooth printing ink.
  • Methanol is highly soluble in water and possesses higher evaporation rate than ethanol.
  • the functionalized colloid is dispersed in ethylene glycol, terpineol and methanol with a volume/volume ratio of 1 : 0.03: 0.005:0.05.
  • the functionalized colloid is dispersed in ethylene glycol and methanol with a volume/volume ratio of 1 : 0.06: 0.1.
  • the combination of said dispersants is employed when the circuit design has the minimum line width of 100 pm.
  • the step of vortexing (112) is carried out at 400 rpm to 500 rpm for 5 minutes.
  • the graphene-conductive polymer dispersion liquid is filtered with a 5 pm filter disc (114) before depositing on the substrate; wherein the substrate is a flexible substrate.
  • the graphene-based conductive film is a reduced graphene oxide-silver nanoparticles conductive film.
  • the functionalized reduced graphene oxide-silver nanoparticles colloid was dispersed to dispersants mixture comprising ethylene glycol, terpineol and methanol with a volume/volume ratio of 1 : 0.03: 0.005:0.05 (110). The addition of dispersants helps to ensure the inkjet printing at the later stage run smoothly without clogging.
  • the functionalized reduced graphene oxide-silver nanoparticles colloid was vortexed at 400 rpm to 500 rpm for 5 minutes to obtain reduced graphene oxide-silver nanoparticles conductive polymer dispersion liquid (112) which is a functionalized reduced graphene oxide-silver nanoparticles ink.
  • the functionalized reduced graphene oxide-silver nanoparticles ink was filtered with a 5 pm filter disc (114). Preparation of reduced graphene oxide-silver nanoparticles conductive film
  • the functionalized reduced graphene oxide-silver nanoparticles ink was injected into an empty cartridge. A detachable nozzle head was attached to the filled cartridge and loaded onto the cartridge stage of the printer. The functionalized reduced graphene oxide-silver nanoparticles ink was then printed on the flexible substrate through inkjet printing to form reduced graphene oxide-silver nanoparticles conductive film (116) with improved hardness.
  • the hardness of reduced graphene oxide-silver nanoparticles conductive film produced using the method (100) of the present invention was evaluated using ASTM D3363 pencil hardness test. Further, the electrical test was carried out to evaluate the resistance, resistivity and conductivity of the film.
  • Table 1 shows the comparative results of the pencil hardness test and electrical test between reduced graphene oxide-silver nanoparticles conductive film of the present invention and the other graphene-based conductive film of the prior art.
  • table 1 shows the reduced graphene oxide-silver nanoparticles conductive film of the present invention exhibits hardness up to 2H as compared to the graphene-based conductive film of the prior art with hardness only up to HB.
  • reduced graphene oxide-silver nanoparticles conductive film of the present invention also shows better electrical performance in terms of resistance, resistivity and conductivity. This result indicates the simpler method (100) of the present invention is workable to produce reduced graphene-based nanoparticles conductive film with improved hardness without degrading its electrical performance.

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Abstract

The present invention discloses a method (100) for preparing a graphene-based conductive film characterized by the steps of: adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid (104); adding dispersants into said functionalized colloid (110); vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid (112); and depositing said graphene-based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film (116).

Description

A METHOD FOR PREPARING A GRAPHENE-BASED CONDUCTIVE FILM
FIELD OF THE INVENTION
The present invention relates to preparation of graphene-based conductive film for flexible electronics, more particularly a method for preparing a reduced graphene oxide-silver nanoparticles conductive film through inkjet printing.
BACKGROUND OF THE INVENTION
Flexible electronics is a technology that allows building of electronic circuits on flexible substrates thus making them foldable and stretchable. The main advantages of flexible electronics are the low cost manufacturing through inkjet printing and inexpensive flexible substrate such as plastics, paper, textiles or metal foils. Therefore, flexible electronic has gained great attention due to its ability in providing cost effective solutions to wide area of applications such as rollable displays, electronic paper, flexible cellular phone, solar cells, RFID-tags, wearable sensors for health monitoring, lab-on-a-chip for disease diagnostics, flexible temperature sensors for healthcare and et cetera.
As the demand for wearable and foldable electronic devices increases rapidly, the conductive film as an important component in the electronic devices is greatly needed. Accordingly, graphene with superior electrical and thermal conductivities has been widely used as a based material in production of conductive film. The production process of graphene-based material such as chemical reduction is usually unable to remove all the oxygen in graphene oxide thereby creating defects and vacancies to produce graphene-based material with lower quality as compared to pristine graphene.
As a result, the graphene-based conductive film produced through inkjet printing is potentially causing several issues. For instance, the film with lower hardness can cause film rupture and thus generate adhesion issue. Consequently, the methods to functionalize graphene-based material such as addition of conductive polymers into graphene-based material have been developed to reinforce the film hardness. Nevertheless, the existing methods also degrade the electrical performance of the film and lead to clogging issue in inkjet printing while increasing the film hardness. Accordingly, an improved method with simpler steps is required in order to effectively address the aforementioned issues.
US20160244577 A1 discloses a method for manufacturing a graphene polymer conductive film. The method comprising the steps of providing a graphene powder and a plurality of conductive monomers; providing a solvent and producing a graphene dispersion liquid by stirring and ultrasonic processing after mixing the graphene powder into the solvent; producing a mixed liquid having the graphene and the conductive monomers by stirring and ultrasonic processing after mixing the conductive monomers into the graphene dispersion liquid; mixing an initiator into the mixed liquid of the graphene and the conductive monomers for in situ polymerization to produce a pre-liquid of a graphene conductive polymer composite material; producing a powder of the graphene conductive polymer composite material by removing solvent and impurity in the pre-liquid of the graphene conductive polymer composite material through a filtration and drying process; providing, mixing and stirring an epoxy resin, a curing agent and an accelerator until uniformly distributed to produce epoxy resin glue system; distributing the powder of the graphene conductive polymer composite material into the epoxy resin glue system to produce a pre-material of the graphene polymer conductive film; and deaerating the pre-material of the graphene polymer conductive film to produce the graphene polymer conductive film.
CN103839608A discloses a method for preparing graphene conductive film. The method comprising the steps of adding graphite or graphite derivative to the dispersant/ethanol/dimethyl formamide organic solvent to obtain dispersion liquid; subjecting the dispersion liquid to high density ultrasonication to obtain a monomolecular layer or a multilayer graphene solution, and the upper layer liquid is taken after high-speed centrifugation, and the graphene powder is obtained after flocculation treatment; dispersing the graphene powder into an organic solvent to prepare an inkjet ink; injecting the inkjet ink into the ink cartridge and deposited onto the pre-processed substrate in a predetermined pattern by conventional inkjet printing technology; drying the conductive film deposited on the substrate in an oven to obtain graphene conductive film.
Jiantong Li et al., Efficient Inkjet Printing of Graphene, Advanced Materials, Volume 25, 29 (2013), 1 -8 discloses a method for preparing graphene conductive film using inkjet printing. The graphene is first exfoliated from graphite flakes in dimethylformamide which is DMF. After that, the low viscosity and toxic DMF is changed to high-viscosity and environmental-friendly terpineol through distillation to concentrating the graphene. Prior to printing, the graphene/terpineol dispersion is mixed with ethanol to optimize the viscosity and surface tension for inkjet printing. The transparent conductive films are fabricated by printing the graphene inks onto untreated glass slides. After printing, the stabilizing polymers can be effectively removed through a simple annealing process.
The aforesaid methods for preparing graphene-based conductive films are complicated as several additional steps such as polymerization process and drying process are required. Indirectly, said additional steps increase the production cost. Additionally, the aforesaid methods involve the use of toxic chemicals that may cause harm to human and environment. It is apparent that the aforesaid prior arts are lacking a simple, cost effective and harmless method for preparing graphene-based conductive film with improved hardness without degrading its electrical performance.
Accordingly, there is a need to provide a simpler, cost effective and harmless method for preparing a graphene-based conductive film which can improve its hardness without degrading its electrical performance.
SUMMARY OF THE INVENTION
It is an objective of the present invention to provide a simpler and cost effective method for preparing graphene-based conductive film. It is also an objective of the present invention to provide a method for preparing graphene-based conductive film with improved hardness without degrading its electrical performance.
It is further an objective of the present invention to provide harmless method for preparing graphene-based conductive film by eliminating the use of toxic chemicals.
Accordingly, these objectives may be achieved by following the teachings of the present invention. The present invention provides a method for preparing a graphene-based conductive film.
The present invention discloses a method for preparing a graphenebased conductive film characterized by the steps of: adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid; adding dispersants into said functionalized colloid; vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid; and depositing said graphene-based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
The manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may have been referred by embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawing illustrates only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
The features, benefits, and advantages of the present invention will become apparent by reference to the following text figure, with like reference numbers referring to like structures across the views, wherein: Figure 1 shows a flow chart of a method (100) for preparing a graphenebased conductive film in accordance to an embodiment of the present invention
DETAILED DESCRIPTION OF THE INVENTION
While the present invention is described herein by way of example using embodiments and illustrative drawings, those skilled in the art will recognize that the invention is not limited to the embodiments of drawing or drawings described, and are not intended to represent the scale of the various components. Further, some components that may form a part of the invention may not be illustrated in certain figures, for ease of illustration, and such omissions do not limit the embodiments outlined in any way. It should be understood that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the scope of the present invention as defined by the appended claim. As used throughout this description, 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). Further, the words "a" or "an" mean "at least one” and the word “plurality” means “one or more” unless otherwise mentioned. Furthermore, the terminology and phraseology used herein is solely used for descriptive purposes and should not be construed as limiting in scope. Language such as "including," "comprising," "having," "containing," or "involving," and variations thereof, is intended to be broad and encompass the subject matter listed thereafter, equivalents, and additional subject matter not recited, and is not intended to exclude other additives, components, integers or steps. Likewise, the term "comprising" is considered synonymous with the terms "including" or "containing" for applicable legal purposes. Any discussion of documents, acts, materials, devices, articles and the like is included in the specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present invention.
In this disclosure, whenever a composition or an element or a group of elements is preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition, element or group of elements with transitional phrases “consisting of”, “consisting”, “selected from the group of consisting of, “including”, or “is” preceding the recitation of the composition, element or group of elements and vice versa.
The present invention is described hereinafter by various embodiments with reference to the accompanying drawing, wherein reference numerals used in the accompanying drawing correspond to the like elements throughout the description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiment set forth herein. Rather, the embodiment is provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art. In the following detailed description, numeric values and ranges are provided for various aspects of the implementations described. These values and ranges are to be treated as examples only, and are not intended to limit the scope of the claims. In addition, a number of materials are identified as suitable for various facets of the implementations. These materials are to be treated as exemplary, and are not intended to limit the scope of the invention.
Referring to the drawing, the invention will now be described in more detail.
A method (100) for preparing a graphene-based conductive film of the present invention encompasses adding of a conductive polymer to functionalize a graphene-based nanoparticles colloid to improve hardness without degrading the electrical performance of the film.
In accordance with an embodiment of the present invention, the method (100) for preparing graphene-based conductive film comprises the steps of adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid (104); adding dispersants into said functionalized colloid (110); vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid (112); and depositing said graphene- based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film (116).
In a preferred embodiment of the present invention, the graphene-based nanoparticles colloid is reduced graphene oxide-silver nanoparticles colloid in a range of 0.08 g/mL to 0.12 g/mL.
In accordance with an embodiment of the present invention, the conductive polymer is selected from the group consisting of polypyrrole, polyanilene and its derivatives, polyindole, more preferably a doped polypyrrole in a range of 0.02% w/v to 0.15% w/v. Doped polypyrrole is a cost efficient conducting polymer with high thermal and chemical stabilities as well as high solubility in water.
In accordance with an embodiment of the present invention, the step of adding conductive polymer (104) further comprises the steps of stirring the colloid mixture at 900 rpm to 1000 rpm at the temperature of 25°C to 30°C for 1 hour (106) after adding conductive polymer; and sonicating the colloid mixture at 55°C to 65°C for 1 hour to obtain said functionalized colloid (108).
In accordance with an embodiment of the present invention, the dispersants are selected from the group consisting of ethylene glycol, terpineol, methanol, ethanol, 2-propanol, cyclohexanone or combination thereof, more preferably a combination of ethylene glycol, terpineol and methanol. Ethylene glycol is a polar solvent that interacts with oxygen functional group on the graphene-based surface to prevent functionalized colloid from aggregation and thus produce a uniform dispersion. Terpineol is a natural oil for enhancing dispersion of functionalized colloid and thus helps in obtaining of a smooth printing ink. Methanol is highly soluble in water and possesses higher evaporation rate than ethanol. As a result, said combination of dispersants enhance the efficiency of in-situ drying of the printed film at the later stage. In a preferred embodiment of the present invention, the functionalized colloid is dispersed in ethylene glycol, terpineol and methanol with a volume/volume ratio of 1 : 0.03: 0.005:0.05.
In another embodiment of the present invention, the functionalized colloid is dispersed in ethylene glycol and methanol with a volume/volume ratio of 1 : 0.06: 0.1. The combination of said dispersants is employed when the circuit design has the minimum line width of 100 pm.
In accordance with an embodiment of the present invention, the step of vortexing (112) is carried out at 400 rpm to 500 rpm for 5 minutes.
In accordance with an embodiment of the present invention, the graphene-conductive polymer dispersion liquid is filtered with a 5 pm filter disc (114) before depositing on the substrate; wherein the substrate is a flexible substrate.
In a preferred embodiment of the present invention, the graphene-based conductive film is a reduced graphene oxide-silver nanoparticles conductive film.
Hereinafter, example of the present invention will be provided for more detailed explanation. The advantages of the present invention may be more readily understood and put into practical effect from these examples. However, it is also to be understood that the following examples are not to limit the scope of the present invention in any way.
EXAMPLE
The overall method (100) for preparing the reduced graphene oxidesilver nanoparticles conductive film in accordance to an embodiment of the present invention is illustrated in Figure 1 . The detailed of each of the steps of the method (100) were described as follows: Preparation of reduced graphene oxide-silver nanoparticles colloid
Deionized water was added into reduced graphene oxide-silver nanoparticles composite to prepare a mixture of 8.0% w/v to 12.0% w/v. The mixture was stirred at 5000 to 6000 rpm for 15 minutes at 25°C to 30°C to obtain reduced graphene oxide-silver nanoparticles colloid (102). Preparation of functionalized reduced graphene oxide-silver nanoparticles colloid
0.02% w/v to 0.15% w/v of doped polypyrrole was added into 0.08 g/mL to 0.12 g/mL of reduced graphene oxide-silver nanoparticles colloid (104). The colloid mixture was stirred at 1000 rpm at the temperature of 25°C to 30°C for 1 hour (106). Said colloid mixture was then sonicated at 60°C for 1 hour to obtain functionalized reduced graphene oxide-silver nanoparticles colloid (108). Preparation of reduced graphene oxide-silver nanoparticles conductive polymer dispersion liquid
The functionalized reduced graphene oxide-silver nanoparticles colloid was dispersed to dispersants mixture comprising ethylene glycol, terpineol and methanol with a volume/volume ratio of 1 : 0.03: 0.005:0.05 (110). The addition of dispersants helps to ensure the inkjet printing at the later stage run smoothly without clogging. The functionalized reduced graphene oxide-silver nanoparticles colloid was vortexed at 400 rpm to 500 rpm for 5 minutes to obtain reduced graphene oxide-silver nanoparticles conductive polymer dispersion liquid (112) which is a functionalized reduced graphene oxide-silver nanoparticles ink. The functionalized reduced graphene oxide-silver nanoparticles ink was filtered with a 5 pm filter disc (114). Preparation of reduced graphene oxide-silver nanoparticles conductive film
The functionalized reduced graphene oxide-silver nanoparticles ink was injected into an empty cartridge. A detachable nozzle head was attached to the filled cartridge and loaded onto the cartridge stage of the printer. The functionalized reduced graphene oxide-silver nanoparticles ink was then printed on the flexible substrate through inkjet printing to form reduced graphene oxide-silver nanoparticles conductive film (116) with improved hardness.
Experiment Result
The hardness of reduced graphene oxide-silver nanoparticles conductive film produced using the method (100) of the present invention was evaluated using ASTM D3363 pencil hardness test. Further, the electrical test was carried out to evaluate the resistance, resistivity and conductivity of the film. Table 1 shows the comparative results of the pencil hardness test and electrical test between reduced graphene oxide-silver nanoparticles conductive film of the present invention and the other graphene-based conductive film of the prior art.
Table 1 : Comparison on the hardness and electrical test data of graphenebased conductive films
Figure imgf000012_0001
ASTM D3363 pencil hardness test standard:
Figure imgf000012_0002
The result in table 1 shows the reduced graphene oxide-silver nanoparticles conductive film of the present invention exhibits hardness up to 2H as compared to the graphene-based conductive film of the prior art with hardness only up to HB. In comparison to the prior art, reduced graphene oxide-silver nanoparticles conductive film of the present invention also shows better electrical performance in terms of resistance, resistivity and conductivity. This result indicates the simpler method (100) of the present invention is workable to produce reduced graphene-based nanoparticles conductive film with improved hardness without degrading its electrical performance.
Various modifications to these embodiments are apparent to those skilled in the art from the description and the accompanying drawings. The principles associated with the various embodiments described herein may be applied to other embodiments. Therefore, the description is not intended to be limited to the embodiments shown along with the accompanying drawings but is to be providing broadest scope of consistent with the principles and the novel and inventive features disclosed or suggested herein. Accordingly, the invention is anticipated to hold on to all other such alternatives, modifications, and variations that fall within the scope of the present invention and appended claim.

Claims

1. A method (100) for preparing a graphene-based conductive film characterized by the steps of: adding conductive polymer into graphene-based nanoparticles colloid to obtain a functionalized colloid (104); adding dispersants into said functionalized colloid (110); vortexing said functionalized colloid to obtain a graphene-based conductive polymer dispersion liquid (112); and depositing said graphene-based conductive polymer dispersion liquid on a substrate to form the graphene-based conductive film (116).
2. The method (100) as claimed in claim 1 , wherein the graphene-based nanoparticles colloid is reduced graphene oxide-silver nanoparticles colloid in a range of 0.08 g/mL to 0.12 g/mL.
3. The method (100) as claimed in claim 1 , wherein the conductive polymer comprising doped polypyrrole in a range of 0.02% w/v to 0.15% w/v.
4. The method (100) as claimed in claim 1 , wherein the step of adding conductive polymer (104) further comprising the steps of: stirring the colloid mixture at 900 rpm to 1000 rpm at the temperature of 25°C to 30°C for 1 hour after adding conductive polymer (106); and sonicating the colloid mixture at 55°C to 65°C for 1 hour to obtain said functionalized colloid (108).
5. The method (100) as claimed in claim 1 , wherein the dispersants is selected from the group consisting of ethylene glycol, terpineol and methanol or combination thereof.
6. The method (100) as claimed in claim 1 , wherein the volume/volume ratio of functionalized colloid to ethylene glycol, terpineol and methanol is 1 : 0.03: 0.005:0.05.
7. The method (100) as claimed in claim 1 , wherein the volume/volume ratio of functionalized colloid to ethylene glycol and methanol is 1 : 0.06: 0.1.
8. The method (100) as claimed in claim 1 , wherein the step of vortexing (112) is carried out at 400 rpm to 500 rpm for 5 minutes.
9. The method (100) as claimed in claim 1 , wherein the graphene-based conductive polymer dispersion liquid is filtered with a 5 pm filter disc (114) before depositing on the substrate.
10. The method (100) as claimed in claim 1 , wherein the graphene-based conductive film is a reduced graphene oxide-silver nanoparticles conductive film.
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