US20100000441A1 - Nano graphene platelet-based conductive inks - Google Patents
Nano graphene platelet-based conductive inks Download PDFInfo
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- US20100000441A1 US20100000441A1 US12/215,813 US21581308A US2010000441A1 US 20100000441 A1 US20100000441 A1 US 20100000441A1 US 21581308 A US21581308 A US 21581308A US 2010000441 A1 US2010000441 A1 US 2010000441A1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
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- 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
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- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- 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
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- 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
- C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
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- 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
- C09D11/52—Electrically conductive inks
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- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0212—Printed circuits or mounted components having integral heating means
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0254—High voltage adaptations; Electrical insulation details; Overvoltage or electrostatic discharge protection ; Arrangements for regulating voltages or for using plural voltages
- H05K1/0257—Overvoltage protection
- H05K1/0259—Electrostatic discharge [ESD] protection
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0092—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive pigments, e.g. paint, ink, tampon printing
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0245—Flakes, flat particles or lamellar particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/032—Materials
- H05K2201/0323—Carbon
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10007—Types of components
- H05K2201/10098—Components for radio transmission, e.g. radio frequency identification [RFID] tag, printed or non-printed antennas
Definitions
- a carbon-based ink typically contains particles of graphite, amorphous carbon, or carbon black (CB) that are suspended in a binder/resin and a solvent. These inks are applied on a substrate surface via a number of deposition techniques, including brush painting, syringe application, inkjet printing, screen printing, and gas assisted spraying. The ink is allowed to dry and the resulting carbon-coated surface, if containing a binder or matrix resin, is subjected to a curing treatment. Further, printing RFID tags is seen as the most likely way to reduce their costs to a point where such tags can be widely used on cost sensitive items, such as food packages. Compared to micron-scaled particles, nano-scaled particles are more amenable to inkjet printing.
- CNTs tend to aggregate together and get entangled with one another due to their high length-to-diameter aspect ratio, making it difficult to disperse CNTs in water, organic solvents, and polymer matrices (for forming nanocomposites).
- the aggregation and entanglement of CNTs also dramatically increase the viscosity of the dispersing liquid [e.g., Refs. 5 and 6], to the extent that inkjet printing of CNT inks is possible only when an exceedingly low CNT concentration is involved.
- processing of CNT-resin nanocomposite is not possible with melt mixing/molding (e.g., via extrusion or injection molding) when CNT loading exceeds 5% by weight [Refs. 7 and 8].
- the present invention provides a nano graphene platelet-based conductive ink comprising: (a) nano graphene platelets (NGPs) wherein each of the platelets comprises a graphene sheet or multiple graphene sheets and the platelets have a thickness no greater than 100 nm, and (b) a liquid medium in which the NGPs are dispersed, wherein the NGPs occupy a proportion of at least 0.001% by volume based on the total ink volume.
- NGPs nano graphene platelets
- An NGP is essentially composed of a sheet of graphene plane or multiple sheets of graphene plane stacked and bonded together.
- Each graphene plane also referred to as a graphene sheet or basal plane, comprises a two-dimensional hexagonal structure of carbon atoms.
- Each platelet has a length and a width parallel to the graphite plane and a thickness orthogonal to the graphite plane.
- the largest dimension is defined as the length, the smallest dimension as the thickness, and the third or intermediate dimension as the width.
- the thickness of an NGP is 100 nanometers (nm) or smaller, with a single-sheet NGP being as thin as 0.34 nm.
- the length and width of a NGP are typically between 1 ⁇ m and 20 ⁇ m, but could be longer or shorter.
- the graphene platelets preferably occupy a proportion of at least 1% by volume (for inkjet printability) and up to 40% by volume (for use in screen printing or other dispensing methods) based on the total ink volume.
- a liquid medium such as water and ethanol
- the presently invented conductive ink is preferably inkjet printable since inkjet printing is a cost-effective way to achieve patterns of various materials on both rigid and flexible substrates.
- Inkjet printing of electrically conductive nano particle-based inks offer a very practical platform for generating electrical components, such as electrodes and interconnects. More preferably, inkjet printing is conducted using a conventional, inexpensive printhead in a common desk-top printer. This type of printer typically requires the viscosity of the ink to be in the range of 3-30 mPa ⁇ S (centi-poise or cP). It is of significance to note that the viscosity of a CNT-based ink can not be in this useful range unless the CNT proportion is exceedingly low.
- the CNT concentration of the ink used by Song, et al. [Ref. 1] was as low as 20 ⁇ g/mL (approximately 0.002% by weight of CNTs in water). With such a low concentration, it would take several repeated printing passes (overwrites) to achieve a desired CNT amount, thickness, or property; e.g., it took 8 overwrites to achieve a sheet resistivity of 20 ⁇ m [FIG. 5 in Ref. 1].
- the presently invented NGP-based ink that can carry a high NGP proportion, yet still maintaining a relatively low viscosity, one or two printing passes are sufficient to attain the same desired properties achieved with 5-20 overwrites using CNT-based inks. This implies that the printing speed of NGP-based inks would be much higher. This is on top of the fact that CNTs are extremely expensive.
- the graphene platelets have an average thickness less than 10 nm and more preferably no greater than 1 nm.
- the conductive ink further comprises a surfactant (or dispersing agent) and/or a binder or matrix material.
- the binder or matrix material may be selected from a thermoplastic, a thermoset resin, a conductive organic substance, a petroleum or coal tar pitch, or a combination thereof.
- the conductive ink may further comprise CNTs in an amount of less than 5% (further preferably less than 1%) by volume based on the total conductive ink volume.
- CNTs may be used to modify the properties of the conductive ink.
- the conductive ink may further comprise a conductive additive selected from the group consisting of carbon nanotubes, carbon nano-fibers, carbon black, fine graphite particles, nano-scaled metal particles, and combinations thereof.
- the conductive ink should have a viscosity less than 500 mPaS ( ⁇ 0.5 PaS).
- a much higher viscosity is acceptable.
- the ink may contain 20% by volume or higher of nano graphene platelets yet still exhibiting a low-shear viscosity value less than 200 PaS. This can not be attained with CNT-based inks.
- Another preferred embodiment of the present invention is a conductive ink composition that, after printing onto a solid substrate to form a solid component, provides a thermal conductivity of at least 10 W/(mK), preferably at least 100 W/(mK), and most preferably at least 200 W/(mK); these are higher than thus far the highest conductivity values for CNT- or NGP-based polymer composites.
- FIG. 1 Resistivity of various printed patterns from NGP- and CNT-based inks as a function of the number of printing passes.
- FIG. 3 The viscosity of several inks containing NGP, CNT, CNT+NGP, and CNT+CB as conductive nano fillers.
- FIG. 4 Thermal conductivity data for NGP- and CNT-based nanocomposites deposited on a solid substrate via inkjet printing.
- SWNTs single-walled carbon nanotubes
- MWNTs multi-walled carbon tubes
- NGPs nano graphene plates
- NGPs and related materials Direct synthesis of the NGP material had not been possible, although the material had been conceptually conceived and theoretically predicted to be capable of exhibiting many novel and useful properties.
- Jang and Huang provided an indirect synthesis approach for preparing NGPs and related materials [Ref. 15].
- the process begins with intercalating lamellar graphite flake particles with an expandable intercalation agent (intercalant), followed by thermally expanding the intercalant to exfoliate the flake particles.
- intercalant expandable intercalation agent
- the exfoliated graphite is then subjected to air milling, ball milling, or ultrasonication for further flake separation and size reduction.
- the presently invented conductive inks can contain oxidized or non-oxidized graphene platelets to meet the property requirements of intended applications.
- the preparation of these two types of NGPs and their inks are further discussed as follows:
- the first step for the preparation of pristine NGPs may involve preparing a laminar material powder containing fine graphite particulates (granules) or flakes, short segments of carbon fiber or graphite fiber, carbon or graphite whiskers, carbon or graphitic nano-fibers, or their mixtures.
- the length and/or diameter of these graphite particles are preferably less than 0.2 mm (200 ⁇ m), further preferably less than 0.01 mm (10 ⁇ m). They can be smaller than 1 ⁇ m.
- the graphite particles are known to typically contain micron- and/or nanometer-scaled graphite crystallites with each crystallite being composed of multiple sheets of graphite plane.
- sodium hexametaphosphate sodium lignosulphonate (e.g., marketed under the trade names Vanisperse CB and Marasperse CBOS-4 from Borregaard LignoTech), sodium sulfate, sodium phosphate, sodium sulfonate, sodium dodecylsulfate, sodium dodecylbezenesulfonate, and TRITON-X.
- Ultrasonic or shearing energy also enables the resulting platelets to be well dispersed in the very liquid medium, producing a homogeneous suspension.
- One major advantage of this approach is that exfoliation, separation, and dispersion are achieved in a single step.
- a monomer, oligomer, or polymer may be added to this suspension to form a suspension that is a precursor to a nanocomposite structure.
- both the length and width of these NGPs could be reduced to smaller than 100 nm in size if so desired.
- the thickness direction or c-axis direction normal to the graphene plane
- the oxidized NGPs prepared with a rotating blade device or ultrasonicator are already dispersed in a liquid, such as water, acetone, alcohol, or other organic solvent. They can be directly used as an ink or, in some cases, subjected to a further formulation procedure; e.g., removing some of the water or solvent, adding some more liquid or other ingredient (e.g., a binder or matrix resin).
- a liquid such as water, acetone, alcohol, or other organic solvent.
- the intercalation treatment using concentrated sulfuric-nitric mixtures have intrinsically introduced many useful functional groups to the edges and surfaces of graphene layers. These groups, such as hydroxyl and carbonyl, facilitate dispersion of oxidized NGPs in a polar liquid, such as water and alcohol for the production of conductive inks.
- NGPs could be dissolved in chloroform, benzene, toluene or other organic solvents after oxidation and subsequent derivatization with thionylchloride and octadecylamine. Partially oxidized NGPs may also undergo reactions with fluorine, alkanes, diazonium salts, or ionic functionalization.
- soluble polymers to NGPs by various methods. For example, we could develop non-covalent association of NGPs with linear polymers such as polyvinyl pyrrolidone and polystyrene sulfonate. The intimate interaction that occurs between the polymer and the NGPs results in an increased dispersability of the graphene platelets in water.
- NTPs Nano-Scaled Graphene Platelets
- a typical procedure for preparing non-oxidized NGP-based conductive inks is described as follows: Five grams of graphite flakes, ground to approximately 10 ⁇ m or less in sizes, were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersing agent, Zonyl® FSO surfactant from DuPont) to obtain a suspension. An ultrasonic energy level of 95 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction for different periods of time: 0.5, 1, 2, and 3 hours. The average thickness of the NGPs prepared was found to be 33 nm, 7.4 nm, 1 nm, and 0.89 nm, respectively.
- the NGPs used were those with an average thickness of 7.4 nm.
- the water content of an ink sample was adjusted by using controlled evaporation (to increase NGP volume fraction in a suspension) or adding water (to dilute it).
- Much thinner NGPs (1 nm) were used for electrical resistivity and thermal conductivity measurements.
- NTPs Nano-Scaled Graphene Platelets
- Graphite oxide was prepared by oxidation of graphite flakes with sulfuric acid, nitrate, and potassium permanganate, at a ratio of 4: 1:0.01 at 30° C., according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957]. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The sample was then washed with 5% HCl solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 7. The intent was to remove all sulfuric and nitric acid residue out of graphite interstices.
- the slurry was spray-dried and stored in a vacuum oven at 60° C. for 24 hours.
- the interlayer spacing of the resulting laminar graphite oxide was determined by the Debye-Scherrer X-ray technique to be approximately 0.73 nm (7.3 ⁇ ), indicating that graphite has been converted into graphite oxide.
- Graphite oxide was placed in a quartz tube, which was then inserted into a three-zone tube furnace pre-set at 1,050° C. and maintained at this temperature for 60 seconds. Nitrogen was continuously introduced into the quartz tube while graphite oxide was exfoliated.
- the resulting graphite oxide worms were then mixed with water and subjected to a shearing treatment using a rotating-blade device (Cowles) for 30 minutes. This procedure led to the formation of oxidized NGP dispersion or ink.
- Conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) PEDOT-PSS
- SWCNT-COOHs carboxyl functionalized single-walled carbon nanotubes
- SWCNT-COOHs were purchased from Sigma-Aldrich (CNT content 90%, carboxylic acid composition 3-6 at %, bundle dimensions 4-5 nm ⁇ 0.5-1.5 ⁇ m).
- 2.5 mg of SWCNT-COOHs were dispersed in 20 ml ethanol by ultrasonic agitation for 20 min. Subsequently, the solution was centrifuged at 3500 rpm for 10 min, and the supernatant solution was separated and centrifuged again. The centrifugation procedure was repeated until a stable dark brown solution was achieved.
- the concentration of SWCNT-COOHs in ethanol was found to be approximately 0.1 g/l, corresponding to slightly less than 0.005% by volume. Ethanol evaporation was used to adjust the CNT volume fraction.
- a range of aqueous/ethanol CNT dispersions were prepared for viscosity and conductivity
- PEDOT-PSS (1.3 wt % in water) was purchased from Sigma-Aldrich and diluted with DI water (polymer solution to DI water ratio of 6:4) to prepare the stock solution.
- the ink was made by mixing 8 ml SWCNT-COOH solution (with a CNT concentration of 0.1 g/l) and 2 ml polymer stock solution with vigorous stirring.
- a reference polymer ink solution was made by adding 2 ml of polymer stock solution to 8 ml of ethanol.
- a reference SWCNT-COOH solution was made by mixing 2 ml of DI water to 8 ml of SWCNT-COOH solution in ethanol.
- the inks containing NGPs prepared in Example 1 and inks containing oxidized NGPs prepared in Example 3 were also inkjet printed.
- NGP solution was mixed with PEDOT-PSS to form an ink.
- Both CNT- and NGP-based inks were adjusted to the maximum concentration, with a zero-shear viscosity of approximately 100 mPaS.
- the printed patterns were made on high gloss photo paper using an inkjet printer (Fast T-Jet Blazer TJB-1650 Printer from US Screen Print & Inkjet Technology with an Epson Pro 4800 Printhead) equipped with a cleaned and re-filled cartridge.
- the printed patterns on photo papers were lines with length and width of 40 mm and 2.5 mm, respectively.
- Pt-electrodes 2.0 ⁇ 4.0 mm 2
- the electrical measurements were carried out using a voltmeter and a source meter (Keithley 2182A Nanovoltmeter and Keithley 2400 Sourcemeter).
- the structure of the printouts was characterized by scanning electron microscopy and transmission electron microscopy.
- the resistivity data of printed patterns are summarized in Table 1 and FIG. 1 .
- FIG. 2 indicates that the viscosity of NGP-based inks is typically orders of magnitude lower than that of CNT-based ink with a comparable filler volume fraction.
- the viscosities of the inks containing 1% and 3% NGPs are much lower than the viscosity of the ink containing 0.4% CNTs.
- the NGP-based ink exhibits a viscosity much lower than that of an ink containing 9% CNTs.
- NGPs being two-dimensional sheets with a nano-scaled third dimension, are capable of alleviating or reducing the tendency for CNTs to form aggregates and entanglements.
- NGP-based inks containing more than 40% by volume of NGPs, albeit exhibiting a relatively low viscosity, is still somewhat beyond the suitable viscosity range of current inkjet printers.
- these high-loading NGP-based inks can still be easily screen printed for microelectronic device applications, or spray-coated (e.g., using a compressed air gun) for coating applications.
- the NGP-based inks also have a utility value as coating materials that provide desired electrical and thermal conductivity.
- NGP-based nanocomposites produced from inkjet printing of corresponding conductive inks are superior to CNT nanocomposites in terms of thermal conductivity enhancement.
- the absolute thermal conductivity values of NGP-polymer composites reach 16 W/(mK) with only 5% NGPs. This thermal conductivity value is significantly higher than the best value thus far reported in the literature (e.g., 7 W/(mK) for 25% NGP-epoxy composite reported by Yu, et al. [Ref. 17]). With 40% of the un-oxidized NGPs, the nanocomposite exhibits an impressive thermal conductivity of 245 W/(mK).
- a preferred embodiment of the present invention is a nano graphene platelet-based conductive ink that is printable, comprising: (a) nano graphene platelets that have an average thickness no greater than 10 nm (preferably no greater than 1 nm), and (b) a liquid medium in which these nano graphene platelets are dispersed, wherein the nano graphene platelets occupy a proportion of at least 0.001% (preferably at least 1%, more preferably at least 3%) by volume based on the total ink volume.
- NGP-based conductive inks include the following:
Abstract
Description
- The present invention relates generally to the field of conductive inks, and more particularly to nano graphene platelet-based inks that are electrically and thermally conductive.
- Conductive inks, particularly carbon-based inks, have been widely used in the manufacture of conducting elements in printed circuits and sensor electrodes. Other major markets for conductive inks include emerging applications, such as displays, backplanes, radio frequency identification (RFID), photovoltaics, lighting, disposable electronics, and memory sensors, as well as traditional thick film applications in which screen printing is used in the creation of PCBs, automobile heaters, EMI shielding, and membrane switches. There is tremendous interest in the field of RFID and printed electronics. This is because major retailers and institutions need to be able to more accurately and efficiently track inventory, and RFID and printed electronics are considered the ideal solution.
- Among various electrically conductive nano particles, silver is commonly considered the material of choice for RFID antennas; but, nano silver particles are very expensive. A carbon-based ink typically contains particles of graphite, amorphous carbon, or carbon black (CB) that are suspended in a binder/resin and a solvent. These inks are applied on a substrate surface via a number of deposition techniques, including brush painting, syringe application, inkjet printing, screen printing, and gas assisted spraying. The ink is allowed to dry and the resulting carbon-coated surface, if containing a binder or matrix resin, is subjected to a curing treatment. Further, printing RFID tags is seen as the most likely way to reduce their costs to a point where such tags can be widely used on cost sensitive items, such as food packages. Compared to micron-scaled particles, nano-scaled particles are more amenable to inkjet printing.
- For printed electronics, all conventional carbon-based conductive particles have one or more shortcomings. For instance, graphite particles are too large in size to be inkjet printable; they easily clog up the dispensing nozzles. Carbon black is not sufficiently conducting and, hence, cannot be used alone as a conductive additive in an ink. Another class of carbon materials that can be inkjet printed is the carbon nano-tube (CNT) [Refs. 1-4]. CNTs, although relatively conducting, are prohibitively expensive. The production of CNTs necessarily involves the use of heavy metal elements as catalysts that are undesirable in many applications and must be removed. The CNTs that contain catalysts tend to undergo sedimentation in a dispersing liquid, which is a highly undesirable feature in a conductive ink. Further, CNTs tend to aggregate together and get entangled with one another due to their high length-to-diameter aspect ratio, making it difficult to disperse CNTs in water, organic solvents, and polymer matrices (for forming nanocomposites). The aggregation and entanglement of CNTs also dramatically increase the viscosity of the dispersing liquid [e.g., Refs. 5 and 6], to the extent that inkjet printing of CNT inks is possible only when an exceedingly low CNT concentration is involved. Similarly, processing of CNT-resin nanocomposite is not possible with melt mixing/molding (e.g., via extrusion or injection molding) when CNT loading exceeds 5% by weight [Refs. 7 and 8].
- Therefore, there is a need for nano particle-containing conductive inks that exhibit the following features: (1) the conductive additives are much less expensive than CNTs; (2) the inks are printable, preferably inkjet printable using a conventional, low-cost printhead; (3) the additives and the resulting printed elements are highly conductive, electrically and/or thermally; (4) the additives can be readily dispersed in a wide range of liquid mediums and do not form a sediment; and (5) the inks can contain a high conductive additive content so that a desired amount or thickness of conductive elements can be dispensed and deposited onto a substrate in one pass or few passes (to avoid or reduce the need for repeated printing passes or overwrites). It is of interest to note that high thermal conductivity is a desirable feature of an additive for microelectronic packaging applications since modern microelectronic devices, when in operation, are generating heat at an ever increasing rate. An additive with a high thermal conductivity provides a more efficient thermal management material.
- The following is a list of references that are related to the prior art:
-
- 1. J. W. Song, “Inkjet Printing of Single-Walled Carbon Nanotubes and Electrical Characterization of the Line Pattern,” Nanotechnology, 19 (2008) 095702 (6 pp).
- 2. T. Mustonen, et al., “Inkjet Printing of Transparent and Conductive Patterns of Single-Walled Carbon Nanotubes and PEDOT-PSS Composites,” Phys. Stat. Sol. (b) 244 (2007) 4336-4340.
- 3. W. R. Small, et al., “Inkjet Deposition and Characterization of Transparent Conducting Electroactive Polyaniline Composite Films with a High Carbon Nanotube Loading Fraction,” J. Materials Chem., 17 (2007) 43594361.
- 4. T. Mustonen, et al., “Controlled Ohmic and Nonlinear Electrical Transport in Ink-printed Single-Wall Carbon Nanotube Films,” Physical Review, B 77 (2008) 125430 (7 pp).
- 5. E. K. Hobbie and D. J. Fry, “Rheology of Concentrated Carbon Nanotube Suspensions,” The J. of Chem. Phys., 126 (2007) 124907 (7 pp).
- 6. I. A. Kinloch, S. A. Roberts, and A. H. Windle, “A Rheological Study of Concentrated Aqueous Nanotube Dispersions,” Polymer, 43 (2002) 7483-7491.
- 7. S. S. Rahatekar, et al., “Optical Microstructure and Viscosity Enhancement for an Epoxy Resin Matrix Containing Multiwall Carbon Nanotubes,” J. Rheol. 50 (5) (2006) 599-610.
- 8. Y. Y. Huang, et al., “Dispersion Rheology of Carbon Nanotubes in a Polymer Matrix,” Physical Review, B 73 (2006) 125422 (9 pp).
- 9. E. S. Kirkor, “Conducting Inks,” U.S. Pat. No. 7,097,788 (Aug. 29, 2006).
- 10. O. Matarredona, et al., “Carbon Nanotune Pastes and Method of Use,” U.S. Pat. No. 7,279,247 (Oct. 9, 2007).
- 11. J. J. Mack, et al., “Chemical Manufacture of Nanostructured Materials,” U.S. Pat. No. 6,872,330 (Mar. 29, 2005).
- 12. M. Hirata and S. Horiuchi, “Thin-Film-Like Particles Having Skeleton Constructed by Carbons and Isolated Films,” U.S. Pat. No. 6,596,396 (Jul. 22, 2003).
- 13. Bor Z. Jang, Aruna Zhamu, and Jiusheng Guo, “Process for Producing Nano-scaled Platelets and Nanocomposites,” U.S. patent pending, Ser. No. 11/509,424 (Aug. 25, 2006).
- 14. Bor Z. Jang, Aruna Zhamu, and Jiusheng Guo, “Mass Production of Nano-scaled Platelets and Products,” U.S. patent pending, Ser. No. 11/526,489 (Sep. 26, 2006).
- 15. B. Z. Jang and W. C. Huang, “Nano-scaled Graphene Plates,” U.S. Pat. No. 7,071,258 (Jul. 04, 2006).
- 16. Aruna Zhamu, Jinjun Shi, Jiusheng Guo and Bor Z. Jang, “Method of Producing Exfoliated Graphite, Flexible Graphite, and Nano-Scaled Graphene Plates,” U.S. patent pending, Ser. No. 11/800,728 (May 08, 2007).
- 17. A. Yu, et al., “Graphite Nanoplatelet-Epoxy Composite Thermal Interface Materials,” J. Physical Chem., C 111 (2007) 7565-7569.
- The present invention provides a nano graphene platelet-based conductive ink comprising: (a) nano graphene platelets (NGPs) wherein each of the platelets comprises a graphene sheet or multiple graphene sheets and the platelets have a thickness no greater than 100 nm, and (b) a liquid medium in which the NGPs are dispersed, wherein the NGPs occupy a proportion of at least 0.001% by volume based on the total ink volume.
- An NGP is essentially composed of a sheet of graphene plane or multiple sheets of graphene plane stacked and bonded together. Each graphene plane, also referred to as a graphene sheet or basal plane, comprises a two-dimensional hexagonal structure of carbon atoms. Each platelet has a length and a width parallel to the graphite plane and a thickness orthogonal to the graphite plane. In an NGP, the largest dimension is defined as the length, the smallest dimension as the thickness, and the third or intermediate dimension as the width. By definition, the thickness of an NGP is 100 nanometers (nm) or smaller, with a single-sheet NGP being as thin as 0.34 nm. The length and width of a NGP are typically between 1 μm and 20 μm, but could be longer or shorter. Several methods have been developed for the production of NGPs [e.g., Refs. 11-15].
- The graphene platelets preferably occupy a proportion of at least 1% by volume (for inkjet printability) and up to 40% by volume (for use in screen printing or other dispensing methods) based on the total ink volume. We have surprisingly observed that up to 60% by volume of NGPs can be easily incorporated into a liquid medium, such as water and ethanol, as opposed to the commonly recognized notion that carbon nanotubes (CNTS) can only be properly dispersed in a liquid for less than 10% by volume.
- The presently invented conductive ink is preferably inkjet printable since inkjet printing is a cost-effective way to achieve patterns of various materials on both rigid and flexible substrates. Inkjet printing of electrically conductive nano particle-based inks offer a very practical platform for generating electrical components, such as electrodes and interconnects. More preferably, inkjet printing is conducted using a conventional, inexpensive printhead in a common desk-top printer. This type of printer typically requires the viscosity of the ink to be in the range of 3-30 mPa·S (centi-poise or cP). It is of significance to note that the viscosity of a CNT-based ink can not be in this useful range unless the CNT proportion is exceedingly low. For instance, the CNT concentration of the ink used by Song, et al. [Ref. 1] was as low as 20 μg/mL (approximately 0.002% by weight of CNTs in water). With such a low concentration, it would take several repeated printing passes (overwrites) to achieve a desired CNT amount, thickness, or property; e.g., it took 8 overwrites to achieve a sheet resistivity of 20 μΩm [FIG. 5 in Ref. 1]. By contrast, with the presently invented NGP-based ink that can carry a high NGP proportion, yet still maintaining a relatively low viscosity, one or two printing passes are sufficient to attain the same desired properties achieved with 5-20 overwrites using CNT-based inks. This implies that the printing speed of NGP-based inks would be much higher. This is on top of the fact that CNTs are extremely expensive.
- Currently, certain type of specialty printer can print an ink with a solution viscosity up to 150 mPa·S and some experimental printers that are still under development can work with a viscosity up to 500 mPa·S. Even with these high-viscosity printers one would still find it difficult, if not impossible, to print CNT-based inks with a CNT content greater than 0.2% by weight since their viscosity will be greater than 1 Pa·S or 1,000 mPa·S. This is not the case with NGP-based inks, which usually exhibit a much lower viscosity compared to their CNT counterparts (with comparable additive weight or volume fractions), to be illustrated later with examples.
- Preferably, the graphene platelets have an average thickness less than 10 nm and more preferably no greater than 1 nm. Preferably, the conductive ink further comprises a surfactant (or dispersing agent) and/or a binder or matrix material. The binder or matrix material may be selected from a thermoplastic, a thermoset resin, a conductive organic substance, a petroleum or coal tar pitch, or a combination thereof.
- The conductive ink may further comprise CNTs in an amount of less than 5% (further preferably less than 1%) by volume based on the total conductive ink volume. In addition to CNTs, several other types of conductive additives may be used to modify the properties of the conductive ink. Hence, in one preferred embodiment, the conductive ink may further comprise a conductive additive selected from the group consisting of carbon nanotubes, carbon nano-fibers, carbon black, fine graphite particles, nano-scaled metal particles, and combinations thereof.
- As indicated earlier, for inkjet printing, the conductive ink should have a viscosity less than 500 mPaS (<0.5 PaS). For the conductive inks intended to be screen printed or spray deposited, a much higher viscosity is acceptable. Surprisingly, the ink may contain 20% by volume or higher of nano graphene platelets yet still exhibiting a low-shear viscosity value less than 200 PaS. This can not be attained with CNT-based inks.
- Another preferred embodiment of the present invention is a conductive ink composition that, after printing onto a solid substrate to form a solid component, provides a thermal conductivity of at least 10 W/(mK), preferably at least 100 W/(mK), and most preferably at least 200 W/(mK); these are higher than thus far the highest conductivity values for CNT- or NGP-based polymer composites.
-
FIG. 1 : Resistivity of various printed patterns from NGP- and CNT-based inks as a function of the number of printing passes. -
FIG. 2 : The viscosity of several NGP- and CNT-containing aqueous dispersions or inks over a range of shear rates. -
FIG. 3 : The viscosity of several inks containing NGP, CNT, CNT+NGP, and CNT+CB as conductive nano fillers. -
FIG. 4 : Thermal conductivity data for NGP- and CNT-based nanocomposites deposited on a solid substrate via inkjet printing. - Since the discovery of single-walled carbon nanotubes (SWNTs) and multi-walled carbon tubes (MWNTs), a large number of potential commercial applications have emerged, including polymeric composites, field emission displays, electrical capacitors, and thermal management materials. Although a number of different techniques have been proposed to manufacture CNT-based materials, the current demand of these materials is still limited due to several factors: First, the high cost of CNTs at this stage of production has discouraged a wider scope of application. Second, the difficulties in handling and dispersing CNTs make their incorporation in useful matrices a challenge. The incompatibility of CNTs with most typical solvents limits their effective handling and widespread use, since, when placed in water or most organic solvents, nanotubes generally quickly fall out of suspension even after strong sonication. Third, while only a very small amount of CNTs may be sufficient to achieve greatly improved properties in some applications, the concentration CNTs used may need to be much higher in other applications. All these three factors have a strong, negative impact on the applications of CNTs in conductive inks.
- Rather than trying to develop much lower-cost processes for CNTs, we have worked diligently to develop alternative nano-scaled carbon materials that exhibit comparable properties, but can be produced in larger quantities and at much lower costs. This development work has led to the discovery of processes for producing individual nano-scaled graphite planes (individual graphene sheets) and stacks of multiple nano-scaled graphene sheets, which are collectively called “nano graphene plates (NGPs).” The structures of NGPs may be best visualized by making a longitudinal scission on the single-wall or multi-wall of a nano-tube along its tube axis direction and then flattening up the resulting sheet or plate. NGPs have become much lower-cost substitutes for carbon nano-tubes or other types of nano-rods for various scientific and engineering applications. The electronic, thermal and mechanical properties of NGP materials have been shown to be comparable or superior to those of carbon nano-tubes.
- Direct synthesis of the NGP material had not been possible, although the material had been conceptually conceived and theoretically predicted to be capable of exhibiting many novel and useful properties. Jang and Huang provided an indirect synthesis approach for preparing NGPs and related materials [Ref. 15]. In most of the methods for making separated graphene platelets, the process begins with intercalating lamellar graphite flake particles with an expandable intercalation agent (intercalant), followed by thermally expanding the intercalant to exfoliate the flake particles. In some methods, the exfoliated graphite is then subjected to air milling, ball milling, or ultrasonication for further flake separation and size reduction. The NGPs prepared by using these methods are graphite oxide platelets since intercalation typically involves heavy oxidation of the flake graphite particles. Thermal and electrical conductivities of these oxidized NGPs or graphite oxide platelets are not as high as those of pristine, non-oxidized NGPs, which can be prepared by a direct ultrasonication method without exposing graphite to intercalation or oxidation [Ref. 16]. It is of significance to note that graphite is usually considered a hydrophobic material and can not be dispersed in a polar liquid such as water. Much to our surprise, direct ultasonication-produced NGPs, albeit being pristine, non-oxidized and non-polar graphene layers, are readily dispersable in water and many other organic solvents, in which NGPs were produced originally.
- The presently invented conductive inks can contain oxidized or non-oxidized graphene platelets to meet the property requirements of intended applications. The preparation of these two types of NGPs and their inks are further discussed as follows:
- Using graphite as an example, the first step for the preparation of pristine NGPs may involve preparing a laminar material powder containing fine graphite particulates (granules) or flakes, short segments of carbon fiber or graphite fiber, carbon or graphite whiskers, carbon or graphitic nano-fibers, or their mixtures. The length and/or diameter of these graphite particles are preferably less than 0.2 mm (200 μm), further preferably less than 0.01 mm (10 μm). They can be smaller than 1 μm. The graphite particles are known to typically contain micron- and/or nanometer-scaled graphite crystallites with each crystallite being composed of multiple sheets of graphite plane.
- The second step comprises dispersing laminar materials (e.g., graphite or graphite oxide particles) in a liquid medium (e.g., water, alcohol, or acetone) to obtain a suspension or slurry with the particles being suspended in the liquid medium. The third step entails subjecting the suspension to direct ultrasonication at a temperature typically between 0° C. and 100° C. Hence, this method obviates the need or possibility to expose the graphite material to a high-temperature, oxidizing environment. Preferably, a dispersing agent or surfactant is used to help uniformly disperse particles in the liquid medium. Most importantly, we have surprisingly found that the dispersing agent or surfactant facilitates the exfoliation and separation of the laminar graphite material. Under comparable processing conditions, a graphite sample containing a surfactant usually results in much thinner platelets compared to a sample containing no surfactant. It also takes a shorter length of time for a surfactant-containing suspension to achieve a desired platelet dimension.
- Surfactants or dispersing agents that can be used include anionic surfactants, non-ionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, fluoro-surfactants, and polymeric surfactants. Particularly useful surfactants for practicing the present invention include DuPont's Zonyl series that entails anionic, cationic, non-ionic, and fluoro-based species. Other useful dispersing agents include sodium hexametaphosphate, sodium lignosulphonate (e.g., marketed under the trade names Vanisperse CB and Marasperse CBOS-4 from Borregaard LignoTech), sodium sulfate, sodium phosphate, sodium sulfonate, sodium dodecylsulfate, sodium dodecylbezenesulfonate, and TRITON-X.
- Ultrasonic or shearing energy also enables the resulting platelets to be well dispersed in the very liquid medium, producing a homogeneous suspension. One major advantage of this approach is that exfoliation, separation, and dispersion are achieved in a single step. A monomer, oligomer, or polymer may be added to this suspension to form a suspension that is a precursor to a nanocomposite structure.
- Oxidized NGPs or graphite oxide platelets may be obtained by intercalation and exfoliation of graphite. Intercalation of graphite to form a graphite intercalation compound (GIC) is well-known in the art. A wide range of intercalants have been used; e.g., (a) a solution of sulfuric acid or sulfuric-phosphoric acid mixture, and an oxidizing agent such as hydrogen peroxide and nitric acid and (b) mixtures of sulfuric acid, nitric acid, and manganese permanganate at various proportions. Typical intercalation times are between one hour and five days. The resulting acid-intercalated graphite may be subjected to repeated washing and neutralizing steps to produce a laminar compound that is essentially graphite oxide. In other words, graphite oxide can be readily produced from acid intercalation of graphite flakes.
- Conventional exfoliation processes for producing graphite worms (interconnected networks of thin graphite flakes) from a graphite material normally include exposing a graphite intercalation compound (GIC) or oxidized graphite to a high temperature environment, most typically between 850 and 1,050° C. These high temperatures were utilized with the purpose of maximizing the expansion of graphite crystallites along the c-axis direction. In some cases, separated NGPs are readily obtained with this treatment, particularly when the graphite has been heavily oxidized. In other cases, the exfoliated product may be subjected to a subsequent mechanical shearing treatment, such as ball milling, air milling, rotating-blade shearing, or ultrasonication. With this treatment, either individual oxidized graphene planes (one-layer NGPs) or stacks of oxidized graphene planes bonded together (multi-layer NGPs) are further reduced in thickness (for multi-layer NGPs), width, and length. In addition to the thickness dimension being nano-scaled, both the length and width of these NGPs could be reduced to smaller than 100 nm in size if so desired. In the thickness direction (or c-axis direction normal to the graphene plane), there may be a small number of graphene planes that are still bonded together through the van der Waal's forces that commonly hold the basal planes together in natural graphite. Typically, there are less than 30 layers (often less than 5 layers) of graphene planes, each with length and width from smaller than 1 μm to 100 μm. We observed that high-energy planetary ball mills and rotating blade shearing devices (e.g., Cowles) were particularly effective in producing nano-scaled graphene plates. Since ball milling and rotating-blade shearing are considered as mass production processes, the present method is capable of producing large quantities of NGP materials cost-effectively. This is in sharp contrast to the production and purification processes of carbon nano-tubes, which are slow and expensive.
- The oxidized NGPs prepared with a rotating blade device or ultrasonicator are already dispersed in a liquid, such as water, acetone, alcohol, or other organic solvent. They can be directly used as an ink or, in some cases, subjected to a further formulation procedure; e.g., removing some of the water or solvent, adding some more liquid or other ingredient (e.g., a binder or matrix resin).
- It may be noted that the intercalation treatment using concentrated sulfuric-nitric mixtures have intrinsically introduced many useful functional groups to the edges and surfaces of graphene layers. These groups, such as hydroxyl and carbonyl, facilitate dispersion of oxidized NGPs in a polar liquid, such as water and alcohol for the production of conductive inks.
- After extensive studies on NGP-solvent interactions, we have observed that NGPs could be dissolved in chloroform, benzene, toluene or other organic solvents after oxidation and subsequent derivatization with thionylchloride and octadecylamine. Partially oxidized NGPs may also undergo reactions with fluorine, alkanes, diazonium salts, or ionic functionalization. Alternatively, we could attach soluble polymers to NGPs by various methods. For example, we could develop non-covalent association of NGPs with linear polymers such as polyvinyl pyrrolidone and polystyrene sulfonate. The intimate interaction that occurs between the polymer and the NGPs results in an increased dispersability of the graphene platelets in water.
- The following examples serve to illustrate the best mode practice of the present invention and should not be construed as limiting the scope of the invention:
- A typical procedure for preparing non-oxidized NGP-based conductive inks is described as follows: Five grams of graphite flakes, ground to approximately 10 μm or less in sizes, were dispersed in 1,000 mL of deionized water (containing 0.1% by weight of a dispersing agent, Zonyl® FSO surfactant from DuPont) to obtain a suspension. An ultrasonic energy level of 95 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction for different periods of time: 0.5, 1, 2, and 3 hours. The average thickness of the NGPs prepared was found to be 33 nm, 7.4 nm, 1 nm, and 0.89 nm, respectively.
- For ink viscosity studies, the NGPs used were those with an average thickness of 7.4 nm. The water content of an ink sample was adjusted by using controlled evaporation (to increase NGP volume fraction in a suspension) or adding water (to dilute it). Suspensions with a range of NGP volume fractions, up to greater than 45%, were prepared. Much thinner NGPs (1 nm) were used for electrical resistivity and thermal conductivity measurements.
- Five grams of graphite flakes, ground to approximately 10 μM or less in sizes, were dispersed in 1,000 mL of deionized water to obtain a suspension. An ultrasonic energy level of 95 W (Branson S450 Ultrasonicator) was used for exfoliation, separation, and size reduction for a period of 2.5 hours. The resulting NGPs, although thicker than those prepared with the assistance of a surfactant, were also well dispersed in water, forming a surfactant-free ink.
- Graphite oxide was prepared by oxidation of graphite flakes with sulfuric acid, nitrate, and potassium permanganate, at a ratio of 4: 1:0.01 at 30° C., according to the method of Hummers [U.S. Pat. No. 2,798,878, Jul. 9, 1957]. Upon completion of the reaction, the mixture was poured into deionized water and filtered. The sample was then washed with 5% HCl solution to remove most of the sulfate ions and residual salt and then repeatedly rinsed with deionized water until the pH of the filtrate was approximately 7. The intent was to remove all sulfuric and nitric acid residue out of graphite interstices. The slurry was spray-dried and stored in a vacuum oven at 60° C. for 24 hours. The interlayer spacing of the resulting laminar graphite oxide was determined by the Debye-Scherrer X-ray technique to be approximately 0.73 nm (7.3 Å), indicating that graphite has been converted into graphite oxide. Graphite oxide was placed in a quartz tube, which was then inserted into a three-zone tube furnace pre-set at 1,050° C. and maintained at this temperature for 60 seconds. Nitrogen was continuously introduced into the quartz tube while graphite oxide was exfoliated. The resulting graphite oxide worms were then mixed with water and subjected to a shearing treatment using a rotating-blade device (Cowles) for 30 minutes. This procedure led to the formation of oxidized NGP dispersion or ink.
- Conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) and carboxyl functionalized single-walled carbon nanotubes (SWCNT-COOHs) were also used in the present study.
- SWCNT-COOHs were purchased from Sigma-Aldrich (CNT content 90%, carboxylic acid composition 3-6 at %, bundle dimensions 4-5 nm×0.5-1.5 μm). First, as a typical procedure, 2.5 mg of SWCNT-COOHs were dispersed in 20 ml ethanol by ultrasonic agitation for 20 min. Subsequently, the solution was centrifuged at 3500 rpm for 10 min, and the supernatant solution was separated and centrifuged again. The centrifugation procedure was repeated until a stable dark brown solution was achieved. The concentration of SWCNT-COOHs in ethanol was found to be approximately 0.1 g/l, corresponding to slightly less than 0.005% by volume. Ethanol evaporation was used to adjust the CNT volume fraction. A range of aqueous/ethanol CNT dispersions were prepared for viscosity and conductivity measurements.
- PEDOT-PSS (1.3 wt % in water) was purchased from Sigma-Aldrich and diluted with DI water (polymer solution to DI water ratio of 6:4) to prepare the stock solution. The ink was made by mixing 8 ml SWCNT-COOH solution (with a CNT concentration of 0.1 g/l) and 2 ml polymer stock solution with vigorous stirring. A reference polymer ink solution was made by adding 2 ml of polymer stock solution to 8 ml of ethanol. Similarly, a reference SWCNT-COOH solution was made by mixing 2 ml of DI water to 8 ml of SWCNT-COOH solution in ethanol.
- For comparison, the inks containing NGPs prepared in Example 1 and inks containing oxidized NGPs prepared in Example 3 were also inkjet printed. In one case, NGP solution was mixed with PEDOT-PSS to form an ink. Both CNT- and NGP-based inks were adjusted to the maximum concentration, with a zero-shear viscosity of approximately 100 mPaS.
- The printed patterns were made on high gloss photo paper using an inkjet printer (Fast T-Jet Blazer TJB-1650 Printer from US Screen Print & Inkjet Technology with an Epson Pro 4800 Printhead) equipped with a cleaned and re-filled cartridge. The printed patterns on photo papers were lines with length and width of 40 mm and 2.5 mm, respectively. For electrical resistivity measurements using the 4-point probe method, Pt-electrodes (2.0×4.0 mm2) having an average thickness of ˜30 nm were sputtered on the printouts with a constant gap spacing of 10.0 mm. The electrical measurements were carried out using a voltmeter and a source meter (Keithley 2182A Nanovoltmeter and Keithley 2400 Sourcemeter). The structure of the printouts was characterized by scanning electron microscopy and transmission electron microscopy.
- The resistivity data of printed patterns are summarized in Table 1 and
FIG. 1 . -
TABLE 1 Resistivity of various printed patterns as a function of the number of printing passes. No. PEDOT-PSS + PEDOT-PSS + Oxidized Prints CNT CNT PEDOT-PSS NGPs NGP NGPs 1 7.5E01 8.50E+01 8.70E+02 2 1.00E+03 1.10E01 1.60E+01 1.30E+02 5 2.00E+02 4.00E+02 1.50E00 3.60E+00 7.20E+01 10 1.50E+02 2.00E+03 2.70E+02 20 3.50E+01 4.20E+02 1.00E+02 30 2.00E+01 1.50E+02 2.60E+01 - It is clear from Table 1 and
FIG. 1 that, with CNT-based inks, the resistivity of printed patterns was still as high as 2,000 kΩ/square even after 10 repeated overwrites and 150 kΩ/square after 30 repeated printing passes. By contrast, NGPs provide a low resistivity of 75 kΩ/square in one print. With some conducting polymer (PEDOT-PSS), the NGP-containing printed patterns also exhibit a relatively low resistivity after just a few repeated printing passes. Further, it is clear that the oxidized NGPs are less conductive than un-oxidized NGPs. - The viscosity of NGP- and CNT-containing aqueous dispersions was also investigated and the data are summarized in
FIG. 2 andFIG. 3 .FIG. 2 indicates that the viscosity of NGP-based inks is typically orders of magnitude lower than that of CNT-based ink with a comparable filler volume fraction. The viscosities of the inks containing 1% and 3% NGPs are much lower than the viscosity of the ink containing 0.4% CNTs. With an NGP content as high as 40%, the NGP-based ink exhibits a viscosity much lower than that of an ink containing 9% CNTs. These are very surprising results considering the fact that NGPs and CNTs are basically identical in chemical compositions (all graphene-based), only the geometry being different—sheet versus tube structures. - It is also highly surprising to observe that, by incorporating a small amount of NGPs in a CNT-based ink, one can significantly reduce the viscosity of the CNT ink. This is illustrated in
FIG. 3 , which demonstrates that an ink containing 5% CNTs and 1% NGPs (totally 6% nano filers) actually has a lower viscosity compared to an ink containing 5% CNTs only. Both samples were prepared under comparable ultrasonication conditions. Presumably, NGPs, being two-dimensional sheets with a nano-scaled third dimension, are capable of alleviating or reducing the tendency for CNTs to form aggregates and entanglements. This is an important observation by itself since this feature enables a greater amount of CNTs to be incorporated in a matrix material, significantly broadening the scope of CNT nanocomposite applications. In contrast, as also shown inFIG. 3 , an additional 1% of carbon black (CB) particles actually slightly increase the viscosity of the CNT-ink. - It may be noted that an ink containing more than 40% by volume of NGPs, albeit exhibiting a relatively low viscosity, is still somewhat beyond the suitable viscosity range of current inkjet printers. However, these high-loading NGP-based inks can still be easily screen printed for microelectronic device applications, or spray-coated (e.g., using a compressed air gun) for coating applications. Hence, the NGP-based inks also have a utility value as coating materials that provide desired electrical and thermal conductivity.
- Other types of fillers, other than CNTs or in combination with CNTs, can be added to NGP-based inks to modify their properties. These include carbon black, metal nano particles, conductive organic species, carbon nano-fibers, etc. These conductive fillers are well-known in the art.
- In order to evaluate the thermal conductivity of NGP-polymer and CNT-polymer nanocomposites obtained by inkjet printing, a series of PEDOT-PSS/CNT and PEDOT-PSS/NGP dispersions were prepared in a way similar to the procedure as described above, but the polymer-to-filler ratio was varied to obtain various diluted inks that are inkjet printable. The inks led to printed nanocomposites with various CNT or NGP contents. It may be noted that the NGPs used in this examples have an average thickness of approximately 1 nm, containing one or few graphene planes per platelet. They have exhibited exceptionally high thermal conductivity. The thermal conductivity data for these printed nanocomposites are summarized in
FIG. 4 . It is clear that NGP-based nanocomposites produced from inkjet printing of corresponding conductive inks are superior to CNT nanocomposites in terms of thermal conductivity enhancement. Furthermore, the absolute thermal conductivity values of NGP-polymer composites reach 16 W/(mK) with only 5% NGPs. This thermal conductivity value is significantly higher than the best value thus far reported in the literature (e.g., 7 W/(mK) for 25% NGP-epoxy composite reported by Yu, et al. [Ref. 17]). With 40% of the un-oxidized NGPs, the nanocomposite exhibits an impressive thermal conductivity of 245 W/(mK). - Hence, a preferred embodiment of the present invention is a nano graphene platelet-based conductive ink that is printable, comprising: (a) nano graphene platelets that have an average thickness no greater than 10 nm (preferably no greater than 1 nm), and (b) a liquid medium in which these nano graphene platelets are dispersed, wherein the nano graphene platelets occupy a proportion of at least 0.001% (preferably at least 1%, more preferably at least 3%) by volume based on the total ink volume.
- To meet the requirements of high electrical and thermal conductivity, it has proven essential to prepare inks from non-oxidized or pristine NGPs. Hence, another highly preferred embodiment of the present invention is a nano graphene platelet-based conductive ink that is printable, comprising: (a) non-oxidized or pristine nano graphene platelets, and (b) a liquid medium in which these nano graphene platelets are dispersed, wherein the nano graphene platelets occupy a proportion of at least 0.001% by volume based on the total ink volume (preferably at least 1%, more preferably at least 3%). Again, the inks containing high NGP loadings (e.g., >40% by volume), albeit not inkjet printable using a current inkjet printhead, can be applied or deposited using techniques such as screen printing.
- The features and benefits of NGP-based conductive inks include the following:
-
- (1) NGPs are much less expensive than nano silver particles (e.g., for RFID antenna application) and carbon nano-tubes (CNTs).
- (2) NGP-based nanocomposites are capable of readily forming a thin film, paper, or coating for electromagnetic interference (EMI) shielding and electrostatic charge dissipation (ESD) applications.
- (3) Due to the ultra-high thermal conductivity of NGPs (5 times more thermally conductive, yet 4 times lower in density compared to copper), a nanocomposite thin film, paper, or coating can be used as a thermal management layer in a densely-packed microelectronic device.
- (4) A high loading of NGPs (up to 75% by wt.) can be incorporated into a polymer matrix, as opposed to up to only 5-10% of CNTs. Both CNTs and CNFs (carbon nano-fibers) have dispersion issues which derive from a high length-to-diameter aspect ratio. CNTs require overcoming van der Waals forces, while both CNTs and their larger-diameter cousins (CNFs) can easily get entangled with one another, or “bird-nested” into bundles which must be dispersed to optimize efficacy in many applications. Hence, the loading of these conductive nano-fillers increases the viscosity of the matrix resin to a level that is not conducive to composite processing or inkjet printing. This is not the case for the NGP-resin systems, wherein the two-dimensional platelets can slide over one another, leading to low resistance to shear flow even at a relatively high NGP proportion. This feature would enable easier application of inks/coatings (e.g., easier inkjet printing of an NGP-containing solution) and more convenient melt processing of polymer nanocomposites containing a high NGP loading.
- (5) For thermal management applications, the anisotropic properties NGPs allow them to move heat directionally, enabling control of the heat transfer. These unique materials have an in-plane two-dimensional thermal conductivity that can be tailored to up to 5,300 W/mK and a through-thickness third dimension conductivity of several W/mK. Competition materials, such as aluminum and copper, move heat in all directions, but due to high contact resistance, they do not transfer heat from components efficiently. Further, NGP-based thermal interface materials (TIM) can be easily cut and molded into intricate shapes, sizes and thickness. More importantly, NGP-TIM can be printed onto solid substrates that have intricate surface profiles or difficult-to-reach spots in a microelectronic device. In addition, NGPs can be combined with plastics, metals or elastomers in finished components.
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Cited By (120)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090087661A1 (en) * | 2007-09-27 | 2009-04-02 | Andreas Eder | Plastic composite material and method for manufacturing said material |
US20100239871A1 (en) * | 2008-12-19 | 2010-09-23 | Vorbeck Materials Corp. | One-part polysiloxane inks and coatings and method of adhering the same to a substrate |
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US20130236715A1 (en) * | 2012-03-08 | 2013-09-12 | Aruna Zhamu | Graphene oxide gel bonded graphene composite films and processes for producing same |
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WO2014064432A1 (en) * | 2012-10-22 | 2014-05-01 | Cambridge Enterprise Limited | Functional inks based on layered materials and printed layered materials |
US20140120399A1 (en) * | 2012-10-25 | 2014-05-01 | The Regents Of The University Of California | Graphene based thermal interface materials and methods of manufacturing the same |
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WO2014072877A2 (en) * | 2012-11-08 | 2014-05-15 | Basf Se | Graphene based screen-printable ink and its use in supercapacitors |
US20140175321A1 (en) * | 2012-12-21 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Resin composition for heat dissipation and heat dissipating substrate manufactured by using the same |
KR20140089624A (en) * | 2012-12-27 | 2014-07-16 | 삼성정밀화학 주식회사 | metal ink composition and fabricating method thereof |
WO2014128316A1 (en) * | 2013-02-19 | 2014-08-28 | Grupo Antolín-Ingeniería, S. A. | Method for obtaining a uniform dispersion of graphene platelets in a liquid, and product obtained in this way |
US20140304153A1 (en) * | 2011-11-10 | 2014-10-09 | Yngve Johnsson | Method and a device for bank note handling |
US8871296B2 (en) * | 2013-03-14 | 2014-10-28 | Nanotek Instruments, Inc. | Method for producing conducting and transparent films from combined graphene and conductive nano filaments |
US20140370269A1 (en) * | 2012-01-31 | 2014-12-18 | The University Of Manchester | Graphene Composites |
CN104292984A (en) * | 2013-07-16 | 2015-01-21 | 安炬科技股份有限公司 | Graphene ink and method for manufacturing graphene circuit |
CN104449377A (en) * | 2014-12-16 | 2015-03-25 | 湖北工业大学 | Graphene conductive coating and preparation method thereof |
US20150159024A1 (en) * | 2011-09-30 | 2015-06-11 | Ppg Industries Ohio, Inc. | Graphenic carbon particle co-dispersions and methods of making same |
DE102013225904A1 (en) | 2013-12-13 | 2015-06-18 | Humboldt-Universität Zu Berlin | Coating agent for producing an electrically conductive layer |
WO2015089026A1 (en) * | 2013-12-09 | 2015-06-18 | Ppg Industries Ohio, Inc. | Graphenic carbon particle dispersions and methods of making same |
US20150191604A1 (en) * | 2014-01-03 | 2015-07-09 | The Boeing Company | Composition and Method for Inhibiting Corrosion of an Anodized Material |
WO2015103563A1 (en) * | 2014-01-05 | 2015-07-09 | Vorbeck Materials | Wearable electronic devices |
CN104962133A (en) * | 2015-06-26 | 2015-10-07 | 西安理工大学 | Nanometer water-based conductive ink and preparation method thereof |
US20150305212A1 (en) * | 2012-10-16 | 2015-10-22 | Università Degli Studi Di Roma "La Sapienza" | Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences |
WO2015160764A1 (en) * | 2014-04-14 | 2015-10-22 | The Board Of Regents Of The University Of Texas System | Graphene-based coatings |
WO2015168308A1 (en) * | 2014-04-29 | 2015-11-05 | Northwestern University | High-resolution patterning of graphene by screen and gravure printing for highly flexible printed electronics |
TWI509882B (en) * | 2011-06-30 | 2015-11-21 | Jieng Tai Internat Electric Corp | Method of forming antenna |
CN105323949A (en) * | 2014-07-14 | 2016-02-10 | 安炬科技股份有限公司 | Graphene printed circuit structure |
US9260308B2 (en) | 2011-04-19 | 2016-02-16 | Graphene Technologies, Inc. | Nanomaterials and process for making the same |
US9324634B2 (en) | 2011-11-08 | 2016-04-26 | International Business Machines Corporation | Semiconductor interconnect structure having a graphene-based barrier metal layer |
US9363932B2 (en) * | 2012-06-11 | 2016-06-07 | Nanotek Instruments, Inc. | Integrated graphene film heat spreader for display devices |
CN105733367A (en) * | 2014-12-10 | 2016-07-06 | 赖中平 | Radio frequency identification tag conductive ink composition, antenna structure, and antenna manufacturing method |
US9397341B2 (en) | 2012-10-10 | 2016-07-19 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
US20160208124A1 (en) * | 2015-01-19 | 2016-07-21 | Chung-Ping Lai | Conductive ink composition and conductive architecture for wireless antenna |
GB2535887A (en) * | 2015-02-27 | 2016-08-31 | Perpetuus Res & Dev Ltd | A particle dispersion |
WO2016085584A3 (en) * | 2014-10-15 | 2016-09-15 | Northwestern University | Graphene-based ink compositions for three-dimensional printing applications |
CN105990675A (en) * | 2015-02-27 | 2016-10-05 | 赖中平 | Wireless antenna prepared by conductive ink without sticker |
CN106147404A (en) * | 2015-04-20 | 2016-11-23 | 赖中平 | Conductive ink constituent and conductive structure for wireless antenna |
US9520598B2 (en) | 2012-10-10 | 2016-12-13 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
WO2017025697A1 (en) * | 2015-08-10 | 2017-02-16 | The University Of Manchester | Electrically conductive materials comprising graphene |
US20170066897A1 (en) * | 2014-05-30 | 2017-03-09 | Graphene Platform Corporation | Graphene composition and graphene molded article |
US20170081537A1 (en) * | 2011-04-22 | 2017-03-23 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US9637674B2 (en) | 2014-07-21 | 2017-05-02 | Baker Hughes Incorporated | Electrically conductive oil-based fluids |
US20170173571A1 (en) * | 2015-12-17 | 2017-06-22 | Soochow University | Composite material used for catalyzing and degrading nitrogen oxide and preparation method and application thereof |
CN106961004A (en) * | 2016-01-12 | 2017-07-18 | Bgt材料有限公司 | The printing graphene laying manufacture method communicated for wireless Wearable |
KR101757084B1 (en) | 2012-09-28 | 2017-07-26 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Electrically conductive coatings containing graphenic carbon particles |
US9786926B2 (en) | 2013-07-17 | 2017-10-10 | Printed Energy Pty Ltd | Printed silver oxide batteries |
CN107261859A (en) * | 2017-06-22 | 2017-10-20 | 浙江工业大学 | A kind of preparation method of graphene oxide/polymer solvent-resistant compound nanofiltration membrane |
US9825305B2 (en) | 2012-07-18 | 2017-11-21 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US9834693B2 (en) | 2011-04-22 | 2017-12-05 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US9890469B2 (en) | 2012-11-26 | 2018-02-13 | Nanotek Instruments, Inc. | Process for unitary graphene layer or graphene single crystal |
US9938416B2 (en) | 2011-09-30 | 2018-04-10 | Ppg Industries Ohio, Inc. | Absorptive pigments comprising graphenic carbon particles |
US20180206341A1 (en) * | 2017-01-12 | 2018-07-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Device having a substrate configured to be thermoformed coupled to an electrically conductive member |
US10030161B2 (en) | 2011-04-22 | 2018-07-24 | Northwestern University | Methods for preparation of concentrated graphene compositions and related composite materials |
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US20180254549A1 (en) * | 2014-12-04 | 2018-09-06 | Chung-Ping Lai | Wireless antenna made from binder-free conductive carbon-based inks |
WO2018176915A1 (en) * | 2017-03-28 | 2018-10-04 | Boe Technology Group Co., Ltd. | Conductive ink, display substrate and fabrication method thereof, and display apparatus |
US10125298B2 (en) | 2013-03-14 | 2018-11-13 | Case Western Reserve University | High thermal conductivity graphite and graphene-containing composites |
GB2562804A (en) * | 2017-05-26 | 2018-11-28 | Graphitene Ltd | Multilayer film for packaging and method of manufacture thereof |
US20180342729A1 (en) * | 2017-05-24 | 2018-11-29 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
US10144212B2 (en) * | 2014-01-31 | 2018-12-04 | The University Of Manchester | Ink formulation |
US10221071B2 (en) | 2012-07-18 | 2019-03-05 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US10233346B2 (en) | 2015-01-19 | 2019-03-19 | Chung-Ping Lai | Conductive ink composition and conductive architecture for wireless antenna |
US10240052B2 (en) | 2011-09-30 | 2019-03-26 | Ppg Industries Ohio, Inc. | Supercapacitor electrodes including graphenic carbon particles |
US10280356B2 (en) | 2014-07-21 | 2019-05-07 | Baker Hughes, A Ge Company, Llc | Electrically conductive oil-based fluids |
US10294375B2 (en) | 2011-09-30 | 2019-05-21 | Ppg Industries Ohio, Inc. | Electrically conductive coatings containing graphenic carbon particles |
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US10396365B2 (en) | 2012-07-18 | 2019-08-27 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
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EP3591012A1 (en) * | 2018-07-05 | 2020-01-08 | Chung-Ping Lai | Conductive ink for use in manufacturing radio frequency identification (rfid) tag antenna and method for manufacturing rfid tag antenna |
US10566482B2 (en) | 2013-01-31 | 2020-02-18 | Global Graphene Group, Inc. | Inorganic coating-protected unitary graphene material for concentrated photovoltaic applications |
US10584254B2 (en) | 2014-05-15 | 2020-03-10 | Northwestern University | Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions |
EP3629405A1 (en) * | 2018-09-27 | 2020-04-01 | Siemens Aktiengesellschaft | Lithium ion accumulator and material and method for producing the same |
US20200168356A1 (en) * | 2018-11-27 | 2020-05-28 | Nanotek Instruments, Inc. | Conducting polymer composite containing ultra-low loading of graphene |
CN111647322A (en) * | 2020-06-27 | 2020-09-11 | 德阳聪源光电科技股份有限公司 | Conductive ink composition for preparing flexible heating film |
CN111671163A (en) * | 2020-07-13 | 2020-09-18 | 诸暨初升新材料科技有限公司 | Preparation method of graphene heat-conducting ceramic heating body of electronic cigarette atomizer |
US10793733B2 (en) | 2015-04-07 | 2020-10-06 | Northwestern University | Ink compositions for fabricating objects from regoliths and methods of forming the objects |
US10813224B2 (en) | 2016-06-10 | 2020-10-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Device with electrically conducting track and method for fabricating the device |
CN111849253A (en) * | 2020-08-07 | 2020-10-30 | 河南墨特石墨烯科技有限公司 | Graphene heating water-based ink and preparation method thereof |
WO2020238144A1 (en) * | 2019-05-31 | 2020-12-03 | 厦门大学 | Plastic electroplating method |
CN112029342A (en) * | 2020-09-25 | 2020-12-04 | 欧菲微电子技术有限公司 | Conductive ink, ultrasonic fingerprint module and electronic equipment |
US10861617B2 (en) | 2012-11-02 | 2020-12-08 | Global Graphene Group, Inc. | Graphene oxide-coated graphitic foil and processes for producing same |
US10919760B2 (en) | 2013-02-14 | 2021-02-16 | Global Graphene Group, Inc. | Process for nano graphene platelet-reinforced composite material |
CN112625508A (en) * | 2021-01-12 | 2021-04-09 | 陕西科技大学 | Preparation method of graphene conductive ink for 3D printing on paper |
US10978216B2 (en) * | 2016-03-30 | 2021-04-13 | Sumitomo Riko Company Limited | Conductive film and method for producing the same |
US11121358B2 (en) | 2017-09-15 | 2021-09-14 | Honda Motor Co., Ltd. | Method for embedding a battery tab attachment in a self-standing electrode without current collector or binder |
US11171324B2 (en) | 2016-03-15 | 2021-11-09 | Honda Motor Co., Ltd. | System and method of producing a composite product |
US11201318B2 (en) | 2017-09-15 | 2021-12-14 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
EP3768784A4 (en) * | 2018-03-20 | 2021-12-22 | Graphite Innovation and Technologies Inc. | Multifunctional coatings for use in wet environments |
US11325833B2 (en) | 2019-03-04 | 2022-05-10 | Honda Motor Co., Ltd. | Composite yarn and method of making a carbon nanotube composite yarn |
US11352258B2 (en) | 2019-03-04 | 2022-06-07 | Honda Motor Co., Ltd. | Multifunctional conductive wire and method of making |
CN114621635A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Graphene-based battery electrode material screen printing conductive ink, and preparation method and application thereof |
US11374214B2 (en) | 2017-07-31 | 2022-06-28 | Honda Motor Co., Ltd. | Self standing electrodes and methods for making thereof |
US11383213B2 (en) | 2016-03-15 | 2022-07-12 | Honda Motor Co., Ltd. | System and method of producing a composite product |
US11539042B2 (en) | 2019-07-19 | 2022-12-27 | Honda Motor Co., Ltd. | Flexible packaging with embedded electrode and method of making |
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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GB2583503A (en) * | 2019-04-30 | 2020-11-04 | !Obac Ltd | Heated floor or wall coating system |
US20220172860A1 (en) * | 2019-06-11 | 2022-06-02 | Bedimensional S.P.A. | Multifunctional product in the form of electrically conductive and/or electrically and/or magnetically polarizable and/or thermally conductive paste or ink or glue, method for the production thereof and use of said product |
CN110194910A (en) * | 2019-06-17 | 2019-09-03 | 新奥石墨烯技术有限公司 | Electric heating ink and preparation method thereof with low-work voltage and farsighted infrared emittance |
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2798878A (en) * | 1954-07-19 | 1957-07-09 | Nat Lead Co | Preparation of graphitic acid |
US5330680A (en) * | 1988-06-08 | 1994-07-19 | Mitsui Mining Company, Limited | Foliated fine graphite particles and method for preparing same |
US6596396B2 (en) * | 2000-08-09 | 2003-07-22 | Mitsubishi Gas Chemical Company, Inc. | Thin-film-like particles having skeleton constructed by carbons and isolated films |
US6872330B2 (en) * | 2002-05-30 | 2005-03-29 | The Regents Of The University Of California | Chemical manufacture of nanostructured materials |
US20050250052A1 (en) * | 2004-05-10 | 2005-11-10 | Nguyen Khe C | Maskless lithography using UV absorbing nano particle |
US7071258B1 (en) * | 2002-10-21 | 2006-07-04 | Nanotek Instruments, Inc. | Nano-scaled graphene plates |
US7097788B2 (en) * | 2003-06-30 | 2006-08-29 | The Board Of Trustees Of The University Of Illinois | Conducting inks |
US20070161163A1 (en) * | 2002-12-26 | 2007-07-12 | Katsura Hirai | Manufacturing method of thin-film transistor, thin-film transistor sheet, and electric circuit |
US7279247B2 (en) * | 2004-01-09 | 2007-10-09 | The Board Of Regents Of The University Of Oklahoma | Carbon nanotube pastes and methods of use |
US20080111110A1 (en) * | 2002-06-14 | 2008-05-15 | Hyperion Catalysis International, Inc. | Electroconductive Carbon Fibril-based Inks and Coatings |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6869760B2 (en) | 1995-01-11 | 2005-03-22 | The Trustees Of Columbia University In The City Of New York | Use of prostate tumor inducing gene for detection of cancer cells |
US7449081B2 (en) * | 2000-06-21 | 2008-11-11 | E. I. Du Pont De Nemours And Company | Process for improving the emission of electron field emitters |
GB0106358D0 (en) * | 2001-03-13 | 2001-05-02 | Printable Field Emitters Ltd | Field emission materials and devices |
CN100438142C (en) * | 2001-09-26 | 2008-11-26 | 三星Sdi株式会社 | Electrode material, method for preparing electrode material, electrode and battery comprising said electrode |
US6927250B2 (en) * | 2002-08-15 | 2005-08-09 | Advanced Energy Technology Inc. | Graphite composites and methods of making such composites |
US20040127621A1 (en) * | 2002-09-12 | 2004-07-01 | Board Of Trustees Of Michigan State University | Expanded graphite and products produced therefrom |
US20060241237A1 (en) * | 2002-09-12 | 2006-10-26 | Board Of Trustees Of Michigan State University | Continuous process for producing exfoliated nano-graphite platelets |
US7097906B2 (en) * | 2003-06-05 | 2006-08-29 | Lockheed Martin Corporation | Pure carbon isotropic alloy of allotropic forms of carbon including single-walled carbon nanotubes and diamond-like carbon |
US20050016714A1 (en) * | 2003-07-09 | 2005-01-27 | Chung Deborah D.L. | Thermal paste for improving thermal contacts |
US7939218B2 (en) * | 2004-12-09 | 2011-05-10 | Nanosys, Inc. | Nanowire structures comprising carbon |
US20070292622A1 (en) * | 2005-08-04 | 2007-12-20 | Rowley Lawrence A | Solvent containing carbon nanotube aqueous dispersions |
US7658901B2 (en) * | 2005-10-14 | 2010-02-09 | The Trustees Of Princeton University | Thermally exfoliated graphite oxide |
US7662321B2 (en) * | 2005-10-26 | 2010-02-16 | Nanotek Instruments, Inc. | Nano-scaled graphene plate-reinforced composite materials and method of producing same |
US7889502B1 (en) * | 2005-11-04 | 2011-02-15 | Graftech International Holdings Inc. | Heat spreading circuit assembly |
US7914844B2 (en) * | 2005-11-18 | 2011-03-29 | Northwestern University | Stable dispersions of polymer-coated graphitic nanoplatelets |
US7604049B2 (en) * | 2005-12-16 | 2009-10-20 | Schlumberger Technology Corporation | Polymeric composites, oilfield elements comprising same, and methods of using same in oilfield applications |
US7566410B2 (en) * | 2006-01-11 | 2009-07-28 | Nanotek Instruments, Inc. | Highly conductive nano-scaled graphene plate nanocomposites |
US8585816B2 (en) * | 2006-05-16 | 2013-11-19 | Cabot Corporation | Low viscosity, high particulate loading dispersions |
US7449133B2 (en) * | 2006-06-13 | 2008-11-11 | Unidym, Inc. | Graphene film as transparent and electrically conducting material |
US20080023066A1 (en) * | 2006-07-28 | 2008-01-31 | Unidym, Inc. | Transparent electrodes formed of metal electrode grids and nanostructure networks |
US20080048152A1 (en) | 2006-08-25 | 2008-02-28 | Jang Bor Z | Process for producing nano-scaled platelets and nanocompsites |
US7785492B1 (en) | 2006-09-26 | 2010-08-31 | Nanotek Instruments, Inc. | Mass production of nano-scaled platelets and products |
US20100052995A1 (en) * | 2006-11-15 | 2010-03-04 | Board Of Trustees Of Michigan State University | Micropatterning of conductive graphite particles using microcontact printing |
US7824651B2 (en) | 2007-05-08 | 2010-11-02 | Nanotek Instruments, Inc. | Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets |
KR101443222B1 (en) * | 2007-09-18 | 2014-09-19 | 삼성전자주식회사 | Graphene pattern and process for preparing the same |
WO2009085015A1 (en) * | 2008-01-03 | 2009-07-09 | National University Of Singapore | Functionalised graphene oxide |
-
2008
- 2008-07-01 US US12/215,813 patent/US20100000441A1/en not_active Abandoned
-
2011
- 2011-07-18 US US13/184,787 patent/US9456497B2/en active Active
-
2016
- 2016-08-19 US US15/241,886 patent/US10362673B2/en active Active
-
2019
- 2019-07-23 US US16/519,275 patent/US11202369B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2798878A (en) * | 1954-07-19 | 1957-07-09 | Nat Lead Co | Preparation of graphitic acid |
US5330680A (en) * | 1988-06-08 | 1994-07-19 | Mitsui Mining Company, Limited | Foliated fine graphite particles and method for preparing same |
US6596396B2 (en) * | 2000-08-09 | 2003-07-22 | Mitsubishi Gas Chemical Company, Inc. | Thin-film-like particles having skeleton constructed by carbons and isolated films |
US6872330B2 (en) * | 2002-05-30 | 2005-03-29 | The Regents Of The University Of California | Chemical manufacture of nanostructured materials |
US20080111110A1 (en) * | 2002-06-14 | 2008-05-15 | Hyperion Catalysis International, Inc. | Electroconductive Carbon Fibril-based Inks and Coatings |
US7071258B1 (en) * | 2002-10-21 | 2006-07-04 | Nanotek Instruments, Inc. | Nano-scaled graphene plates |
US20070161163A1 (en) * | 2002-12-26 | 2007-07-12 | Katsura Hirai | Manufacturing method of thin-film transistor, thin-film transistor sheet, and electric circuit |
US7097788B2 (en) * | 2003-06-30 | 2006-08-29 | The Board Of Trustees Of The University Of Illinois | Conducting inks |
US7279247B2 (en) * | 2004-01-09 | 2007-10-09 | The Board Of Regents Of The University Of Oklahoma | Carbon nanotube pastes and methods of use |
US20050250052A1 (en) * | 2004-05-10 | 2005-11-10 | Nguyen Khe C | Maskless lithography using UV absorbing nano particle |
Cited By (193)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8034443B2 (en) * | 2007-09-27 | 2011-10-11 | C-Polymers Gmbh | Plastic composite material and method for manufacturing said material |
US20090087661A1 (en) * | 2007-09-27 | 2009-04-02 | Andreas Eder | Plastic composite material and method for manufacturing said material |
US20100239871A1 (en) * | 2008-12-19 | 2010-09-23 | Vorbeck Materials Corp. | One-part polysiloxane inks and coatings and method of adhering the same to a substrate |
US20110088931A1 (en) * | 2009-04-06 | 2011-04-21 | Vorbeck Materials Corp. | Multilayer Coatings and Coated Articles |
US20130005917A1 (en) * | 2009-07-27 | 2013-01-03 | Aruna Zhamu | Process for producing chemically functionalized nano graphene materials |
US8986512B2 (en) * | 2009-07-27 | 2015-03-24 | Nanotek Instruments, Inc. | Process for producing chemically functionalized nano graphene materials |
US20110046289A1 (en) * | 2009-08-20 | 2011-02-24 | Aruna Zhamu | Pristine nano graphene-modified tires |
US7999027B2 (en) * | 2009-08-20 | 2011-08-16 | Nanotek Instruments, Inc. | Pristine nano graphene-modified tires |
US8377408B2 (en) | 2010-04-20 | 2013-02-19 | High Temperature Physics, Llc | Process for the production of carbon nanoparticles and sequestration of carbon |
US20120058255A1 (en) * | 2010-09-08 | 2012-03-08 | Nanyang Technological University | Carbon nanotube-conductive polymer composites, methods of making and articles made therefrom |
US8420042B2 (en) | 2010-09-21 | 2013-04-16 | High Temperature Physics, Llc | Process for the production of carbon graphenes and other nanomaterials |
WO2012112027A1 (en) | 2010-12-06 | 2012-08-23 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Hybrid materials for printing (semi-) conductive elements |
EP2461655A1 (en) * | 2010-12-06 | 2012-06-06 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Hybrid materials for printing conductive or semiconductive elements |
CN103314133A (en) * | 2010-12-08 | 2013-09-18 | 3M创新有限公司 | Article and method of making and using the same |
WO2012078464A3 (en) * | 2010-12-08 | 2012-08-16 | 3M Innovative Properties Company | Article and method of making and using the same |
WO2012078464A2 (en) * | 2010-12-08 | 2012-06-14 | 3M Innovative Properties Company | Article and method of making and using the same |
EP2649217A4 (en) * | 2010-12-08 | 2014-11-26 | 3M Innovative Properties Co | Article and method of making and using the same |
US9321254B2 (en) | 2010-12-08 | 2016-04-26 | 3M Innovative Properties Company | Article and method of making and using the same |
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US8623938B2 (en) * | 2010-12-31 | 2014-01-07 | Tsinghua University | Inkjet ink and method for making the same |
US20120172496A1 (en) * | 2010-12-31 | 2012-07-05 | Hon Hai Precision Industry Co., Ltd. | Inkjet ink and method for making the same |
US20120176244A1 (en) * | 2011-01-07 | 2012-07-12 | Southern Imperial, Inc. | System and Method for Integrated Product Protection |
US9672711B2 (en) * | 2011-01-07 | 2017-06-06 | Southern Imperial, Inc. | System and method for integrated product protection |
US9260308B2 (en) | 2011-04-19 | 2016-02-16 | Graphene Technologies, Inc. | Nanomaterials and process for making the same |
US10800939B2 (en) | 2011-04-22 | 2020-10-13 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US10590294B2 (en) | 2011-04-22 | 2020-03-17 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US10494536B2 (en) | 2011-04-22 | 2019-12-03 | Northwestern University | Methods for preparation of concentrated graphene compositions and related composite materials |
US20170081537A1 (en) * | 2011-04-22 | 2017-03-23 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US9902866B2 (en) * | 2011-04-22 | 2018-02-27 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US10030161B2 (en) | 2011-04-22 | 2018-07-24 | Northwestern University | Methods for preparation of concentrated graphene compositions and related composite materials |
US9834693B2 (en) | 2011-04-22 | 2017-12-05 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US10676629B2 (en) | 2011-04-22 | 2020-06-09 | Northwestern University | Methods for preparation of concentrated graphene ink compositions and related composite materials |
US8167190B1 (en) * | 2011-05-06 | 2012-05-01 | Lockheed Martin Corporation | Electrically conductive polymer compositions containing metal particles and a graphene and methods for production and use thereof |
TWI509882B (en) * | 2011-06-30 | 2015-11-21 | Jieng Tai Internat Electric Corp | Method of forming antenna |
WO2013026827A1 (en) | 2011-08-22 | 2013-02-28 | Bayer Intellectual Property Gmbh | Dispersion comprising carbon nanotubes and graphene platelets |
KR20140054094A (en) * | 2011-08-22 | 2014-05-08 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | Dispersion comprising carbon nanotubes and graphene platelets |
JP2014525981A (en) * | 2011-08-22 | 2014-10-02 | フューチャー カーボン ゲーエムベーハー | Dispersion containing carbon nanotubes and graphene platelets |
EP2562766A1 (en) | 2011-08-22 | 2013-02-27 | Bayer MaterialScience AG | Dispersions containing carbon nanotubes and graphene platelets |
CN103733271A (en) * | 2011-08-22 | 2014-04-16 | 拜耳知识产权有限责任公司 | Dispersion comprising carbon nanotubes and graphene platelets |
US9868875B2 (en) | 2011-08-22 | 2018-01-16 | Futurecarbon Gmbh | Dispersion comprising carbon nanotubes and graphene platelets |
KR102111174B1 (en) * | 2011-08-22 | 2020-05-14 | 푸투레 카르본 게엠베하 | Dispersion comprising carbon nanotubes and graphene platelets |
WO2013036272A1 (en) * | 2011-09-09 | 2013-03-14 | Board Of Trustees Of Northern Illinois University | Crystalline graphene and method of making crystalline graphene |
CN103906706A (en) * | 2011-09-09 | 2014-07-02 | 北伊利诺斯大学董事会 | Crystalline graphene and method of making crystalline graphene |
US9340430B2 (en) | 2011-09-09 | 2016-05-17 | Board Of Trustees Of Northern Illinois University | Crystalline graphene and method of making crystalline graphene |
JP2014527950A (en) * | 2011-09-09 | 2014-10-23 | ボード オブ トラスティーズ オブノーザン イリノイ ユニバーシティー | Crystalline graphene and method for producing crystalline graphene |
EP2570462A1 (en) | 2011-09-19 | 2013-03-20 | Instytut Technologii Materialów Elektronicznych | Method of producing graphene layers and paste comprising graphene nanoplatelets |
WO2013040636A1 (en) * | 2011-09-19 | 2013-03-28 | University Of Wollongong | Reduced graphene oxide and method of producing same |
US9938416B2 (en) | 2011-09-30 | 2018-04-10 | Ppg Industries Ohio, Inc. | Absorptive pigments comprising graphenic carbon particles |
US10294375B2 (en) | 2011-09-30 | 2019-05-21 | Ppg Industries Ohio, Inc. | Electrically conductive coatings containing graphenic carbon particles |
US10240052B2 (en) | 2011-09-30 | 2019-03-26 | Ppg Industries Ohio, Inc. | Supercapacitor electrodes including graphenic carbon particles |
US20150159024A1 (en) * | 2011-09-30 | 2015-06-11 | Ppg Industries Ohio, Inc. | Graphenic carbon particle co-dispersions and methods of making same |
US9475946B2 (en) * | 2011-09-30 | 2016-10-25 | Ppg Industries Ohio, Inc. | Graphenic carbon particle co-dispersions and methods of making same |
US9324635B2 (en) | 2011-11-08 | 2016-04-26 | International Business Machines Corporation | Semiconductor interconnect structure having a graphene-based barrier metal layer |
US9324634B2 (en) | 2011-11-08 | 2016-04-26 | International Business Machines Corporation | Semiconductor interconnect structure having a graphene-based barrier metal layer |
US20140304153A1 (en) * | 2011-11-10 | 2014-10-09 | Yngve Johnsson | Method and a device for bank note handling |
US20140370269A1 (en) * | 2012-01-31 | 2014-12-18 | The University Of Manchester | Graphene Composites |
US11254799B2 (en) * | 2012-01-31 | 2022-02-22 | The University Of Manchester | Graphene composites |
US20130236715A1 (en) * | 2012-03-08 | 2013-09-12 | Aruna Zhamu | Graphene oxide gel bonded graphene composite films and processes for producing same |
US9561955B2 (en) * | 2012-03-08 | 2017-02-07 | Nanotek Instruments, Inc. | Graphene oxide gel bonded graphene composite films and processes for producing same |
US9363932B2 (en) * | 2012-06-11 | 2016-06-07 | Nanotek Instruments, Inc. | Integrated graphene film heat spreader for display devices |
EP2682724A1 (en) * | 2012-07-04 | 2014-01-08 | Sensing Tex, S.L. | A large-area extensible pressure sensor for textiles surfaces |
CN103528722A (en) * | 2012-07-04 | 2014-01-22 | 特克斯传感有限公司 | A large-area extensible pressure sensor for textiles surfaces |
US10109864B2 (en) | 2012-07-18 | 2018-10-23 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US11673811B2 (en) | 2012-07-18 | 2023-06-13 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US10396365B2 (en) | 2012-07-18 | 2019-08-27 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US11637292B2 (en) | 2012-07-18 | 2023-04-25 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US9825305B2 (en) | 2012-07-18 | 2017-11-21 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US10770733B2 (en) | 2012-07-18 | 2020-09-08 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US11063265B2 (en) | 2012-07-18 | 2021-07-13 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US10221071B2 (en) | 2012-07-18 | 2019-03-05 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
US11066306B2 (en) | 2012-07-18 | 2021-07-20 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
KR101757084B1 (en) | 2012-09-28 | 2017-07-26 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Electrically conductive coatings containing graphenic carbon particles |
US10658679B2 (en) | 2012-10-10 | 2020-05-19 | Printed Energy Pty Ltd | Printed energy storage device |
US9520598B2 (en) | 2012-10-10 | 2016-12-13 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
US9397341B2 (en) | 2012-10-10 | 2016-07-19 | Nthdegree Technologies Worldwide Inc. | Printed energy storage device |
US10686197B2 (en) | 2012-10-10 | 2020-06-16 | Printed Energy Pty Ltd | Printed energy storage device |
US9917309B2 (en) | 2012-10-10 | 2018-03-13 | Printed Energy Pty Ltd | Printed energy storage device |
US11502311B2 (en) | 2012-10-10 | 2022-11-15 | Printed Energy Pty Ltd | Printed energy storage device |
US10020516B2 (en) | 2012-10-10 | 2018-07-10 | Printed Energy Pty Ltd | Printed energy storage device |
US20150305212A1 (en) * | 2012-10-16 | 2015-10-22 | Università Degli Studi Di Roma "La Sapienza" | Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences |
US9717170B2 (en) * | 2012-10-16 | 2017-07-25 | Universita Degli Studi Di Roma “La Sapienza” | Graphene nanoplatelets- or graphite nanoplatelets-based nanocomposites for reducing electromagnetic interferences |
WO2014064432A1 (en) * | 2012-10-22 | 2014-05-01 | Cambridge Enterprise Limited | Functional inks based on layered materials and printed layered materials |
US9718972B2 (en) | 2012-10-22 | 2017-08-01 | Cambridge Enterprise Limited | Functional inks based on layered materials and printed layered materials |
JP2015537074A (en) * | 2012-10-22 | 2015-12-24 | ケンブリッジ エンタープライズ リミテッド | Functional ink based on layered material and printed layered material |
US9716299B2 (en) * | 2012-10-25 | 2017-07-25 | The Regents Of The University Of California | Graphene based thermal interface materials and methods of manufacturing the same |
US20140120399A1 (en) * | 2012-10-25 | 2014-05-01 | The Regents Of The University Of California | Graphene based thermal interface materials and methods of manufacturing the same |
US9803097B2 (en) | 2012-10-29 | 2017-10-31 | 3M Innovative Properties Company | Conductive inks and conductive polymeric coatings |
WO2014070500A1 (en) * | 2012-10-29 | 2014-05-08 | 3M Innovative Properties Company | Conductive inks and conductive polymeric coatings |
US10861617B2 (en) | 2012-11-02 | 2020-12-08 | Global Graphene Group, Inc. | Graphene oxide-coated graphitic foil and processes for producing same |
WO2014072877A2 (en) * | 2012-11-08 | 2014-05-15 | Basf Se | Graphene based screen-printable ink and its use in supercapacitors |
WO2014072877A3 (en) * | 2012-11-08 | 2014-07-03 | Basf Se | Graphene based screen-printable ink and its use in supercapacitors |
US10161056B2 (en) | 2012-11-26 | 2018-12-25 | Nanotek Instruments, Inc. | Heat dissipation system comprising a unitary graphene monolith |
US9890469B2 (en) | 2012-11-26 | 2018-02-13 | Nanotek Instruments, Inc. | Process for unitary graphene layer or graphene single crystal |
US20140175321A1 (en) * | 2012-12-21 | 2014-06-26 | Samsung Electro-Mechanics Co., Ltd. | Resin composition for heat dissipation and heat dissipating substrate manufactured by using the same |
KR20140089624A (en) * | 2012-12-27 | 2014-07-16 | 삼성정밀화학 주식회사 | metal ink composition and fabricating method thereof |
CN103013229A (en) * | 2012-12-30 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Graphene based conductive ink and preparation method thereof as well as flexible conductive thin film |
US10566482B2 (en) | 2013-01-31 | 2020-02-18 | Global Graphene Group, Inc. | Inorganic coating-protected unitary graphene material for concentrated photovoltaic applications |
US10919760B2 (en) | 2013-02-14 | 2021-02-16 | Global Graphene Group, Inc. | Process for nano graphene platelet-reinforced composite material |
WO2014128316A1 (en) * | 2013-02-19 | 2014-08-28 | Grupo Antolín-Ingeniería, S. A. | Method for obtaining a uniform dispersion of graphene platelets in a liquid, and product obtained in this way |
CN103113786A (en) * | 2013-03-07 | 2013-05-22 | 苏州牛剑新材料有限公司 | Graphene conductive ink and preparation method thereof |
US8871296B2 (en) * | 2013-03-14 | 2014-10-28 | Nanotek Instruments, Inc. | Method for producing conducting and transparent films from combined graphene and conductive nano filaments |
US10125298B2 (en) | 2013-03-14 | 2018-11-13 | Case Western Reserve University | High thermal conductivity graphite and graphene-containing composites |
CN104292984A (en) * | 2013-07-16 | 2015-01-21 | 安炬科技股份有限公司 | Graphene ink and method for manufacturing graphene circuit |
US10673077B2 (en) | 2013-07-17 | 2020-06-02 | Printed Energy Pty Ltd | Printed silver oxide batteries |
US9786926B2 (en) | 2013-07-17 | 2017-10-10 | Printed Energy Pty Ltd | Printed silver oxide batteries |
CN103436074A (en) * | 2013-08-05 | 2013-12-11 | 南昌大学 | Preparation method of water-based conductive ink |
JP5490957B1 (en) * | 2013-10-25 | 2014-05-14 | 清二 加川 | Heat dissipation film, and method and apparatus for manufacturing the same |
US9574094B2 (en) * | 2013-12-09 | 2017-02-21 | Ppg Industries Ohio, Inc. | Graphenic carbon particle dispersions and methods of making same |
WO2015089026A1 (en) * | 2013-12-09 | 2015-06-18 | Ppg Industries Ohio, Inc. | Graphenic carbon particle dispersions and methods of making same |
RU2627411C1 (en) * | 2013-12-09 | 2017-08-08 | Ппг Индастриз Огайо, Инк. | Dispersions of graphene carbon particles and method for their production |
CN105917419A (en) * | 2013-12-09 | 2016-08-31 | Ppg工业俄亥俄公司 | Graphene carbon particle dispersions and methods of making same |
DE102013225904A1 (en) | 2013-12-13 | 2015-06-18 | Humboldt-Universität Zu Berlin | Coating agent for producing an electrically conductive layer |
US20150191604A1 (en) * | 2014-01-03 | 2015-07-09 | The Boeing Company | Composition and Method for Inhibiting Corrosion of an Anodized Material |
CN106029956A (en) * | 2014-01-03 | 2016-10-12 | 波音公司 | Composition and method for inhibiting corrosion of an anodized material |
US9771481B2 (en) * | 2014-01-03 | 2017-09-26 | The Boeing Company | Composition and method for inhibiting corrosion of an anodized material |
WO2015103563A1 (en) * | 2014-01-05 | 2015-07-09 | Vorbeck Materials | Wearable electronic devices |
US10144212B2 (en) * | 2014-01-31 | 2018-12-04 | The University Of Manchester | Ink formulation |
WO2015160764A1 (en) * | 2014-04-14 | 2015-10-22 | The Board Of Regents Of The University Of Texas System | Graphene-based coatings |
WO2015168308A1 (en) * | 2014-04-29 | 2015-11-05 | Northwestern University | High-resolution patterning of graphene by screen and gravure printing for highly flexible printed electronics |
US9840634B2 (en) | 2014-04-29 | 2017-12-12 | Northwestern University | High-resolution patterning of graphene by screen and gravure printing for highly flexible printed electronics |
US10479905B2 (en) | 2014-04-29 | 2019-11-19 | Northwestern University | High-resolution patterning of graphene by screen and gravure printing for highly flexible printed electronics |
US11459473B2 (en) | 2014-05-15 | 2022-10-04 | Northwestern University | Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions |
US10584254B2 (en) | 2014-05-15 | 2020-03-10 | Northwestern University | Ink compositions for three-dimensional printing and methods of forming objects using the ink compositions |
US20170066897A1 (en) * | 2014-05-30 | 2017-03-09 | Graphene Platform Corporation | Graphene composition and graphene molded article |
US9745441B2 (en) * | 2014-05-30 | 2017-08-29 | Graphene Platform Corporation | Graphene composition and graphene molded article |
US9460828B2 (en) * | 2014-07-14 | 2016-10-04 | Enerage Inc. | Graphene printed pattern circuit structure |
CN105323949A (en) * | 2014-07-14 | 2016-02-10 | 安炬科技股份有限公司 | Graphene printed circuit structure |
US10280356B2 (en) | 2014-07-21 | 2019-05-07 | Baker Hughes, A Ge Company, Llc | Electrically conductive oil-based fluids |
US9637674B2 (en) | 2014-07-21 | 2017-05-02 | Baker Hughes Incorporated | Electrically conductive oil-based fluids |
US10611947B2 (en) | 2014-07-21 | 2020-04-07 | Baker Hughes, A Ge Company, Llc | Electrically conductive oil-based fluids |
US10350329B2 (en) | 2014-10-15 | 2019-07-16 | Northwestern University | Graphene-based ink compositions for three-dimensional printing applications |
WO2016085584A3 (en) * | 2014-10-15 | 2016-09-15 | Northwestern University | Graphene-based ink compositions for three-dimensional printing applications |
US20180254549A1 (en) * | 2014-12-04 | 2018-09-06 | Chung-Ping Lai | Wireless antenna made from binder-free conductive carbon-based inks |
CN105733367A (en) * | 2014-12-10 | 2016-07-06 | 赖中平 | Radio frequency identification tag conductive ink composition, antenna structure, and antenna manufacturing method |
CN104449377A (en) * | 2014-12-16 | 2015-03-25 | 湖北工业大学 | Graphene conductive coating and preparation method thereof |
US20160208124A1 (en) * | 2015-01-19 | 2016-07-21 | Chung-Ping Lai | Conductive ink composition and conductive architecture for wireless antenna |
US10233346B2 (en) | 2015-01-19 | 2019-03-19 | Chung-Ping Lai | Conductive ink composition and conductive architecture for wireless antenna |
CN105990675A (en) * | 2015-02-27 | 2016-10-05 | 赖中平 | Wireless antenna prepared by conductive ink without sticker |
GB2535887A (en) * | 2015-02-27 | 2016-08-31 | Perpetuus Res & Dev Ltd | A particle dispersion |
US10793733B2 (en) | 2015-04-07 | 2020-10-06 | Northwestern University | Ink compositions for fabricating objects from regoliths and methods of forming the objects |
CN106147404A (en) * | 2015-04-20 | 2016-11-23 | 赖中平 | Conductive ink constituent and conductive structure for wireless antenna |
CN104962133A (en) * | 2015-06-26 | 2015-10-07 | 西安理工大学 | Nanometer water-based conductive ink and preparation method thereof |
WO2017025697A1 (en) * | 2015-08-10 | 2017-02-16 | The University Of Manchester | Electrically conductive materials comprising graphene |
US11648731B2 (en) | 2015-10-29 | 2023-05-16 | Hewlett-Packard Development Company, L.P. | Forming three-dimensional (3D) printed electronics |
US10441945B2 (en) * | 2015-12-17 | 2019-10-15 | Soochow University | Composite material used for catalyzing and degrading nitrogen oxide and preparation method and application thereof |
US20170173571A1 (en) * | 2015-12-17 | 2017-06-22 | Soochow University | Composite material used for catalyzing and degrading nitrogen oxide and preparation method and application thereof |
CN106961004A (en) * | 2016-01-12 | 2017-07-18 | Bgt材料有限公司 | The printing graphene laying manufacture method communicated for wireless Wearable |
US11888152B2 (en) | 2016-03-15 | 2024-01-30 | Honda Motor Co., Ltd. | System and method of producing a composite product |
US11383213B2 (en) | 2016-03-15 | 2022-07-12 | Honda Motor Co., Ltd. | System and method of producing a composite product |
US11171324B2 (en) | 2016-03-15 | 2021-11-09 | Honda Motor Co., Ltd. | System and method of producing a composite product |
US10978216B2 (en) * | 2016-03-30 | 2021-04-13 | Sumitomo Riko Company Limited | Conductive film and method for producing the same |
US10813224B2 (en) | 2016-06-10 | 2020-10-20 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Device with electrically conducting track and method for fabricating the device |
US11019729B2 (en) * | 2017-01-12 | 2021-05-25 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Device having a substrate configured to be thermoformed coupled to an electrically conductive member |
US20180206341A1 (en) * | 2017-01-12 | 2018-07-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Device having a substrate configured to be thermoformed coupled to an electrically conductive member |
US10442945B2 (en) | 2017-03-28 | 2019-10-15 | Boe Technology Group Co., Ltd. | Conductive ink, display substrate and fabrication method thereof, and display apparatus |
WO2018176915A1 (en) * | 2017-03-28 | 2018-10-04 | Boe Technology Group Co., Ltd. | Conductive ink, display substrate and fabrication method thereof, and display apparatus |
US11081684B2 (en) * | 2017-05-24 | 2021-08-03 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
US11735705B2 (en) | 2017-05-24 | 2023-08-22 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
US20180342729A1 (en) * | 2017-05-24 | 2018-11-29 | Honda Motor Co., Ltd. | Production of carbon nanotube modified battery electrode powders via single step dispersion |
GB2562804B (en) * | 2017-05-26 | 2019-09-25 | Graphitene Ltd | Multilayer film for packaging and method of manufacture thereof |
GB2562804A (en) * | 2017-05-26 | 2018-11-28 | Graphitene Ltd | Multilayer film for packaging and method of manufacture thereof |
CN107261859A (en) * | 2017-06-22 | 2017-10-20 | 浙江工业大学 | A kind of preparation method of graphene oxide/polymer solvent-resistant compound nanofiltration membrane |
RU2665397C1 (en) * | 2017-07-06 | 2018-08-29 | Федеральное государственное бюджетное учреждение науки Институт физики полупроводников им. А.В. Ржанова Сибирского отделения Российской академии наук (ИФП СО РАН) | Graphene aqueous suspension for conductive ink production method |
US11374214B2 (en) | 2017-07-31 | 2022-06-28 | Honda Motor Co., Ltd. | Self standing electrodes and methods for making thereof |
US11569490B2 (en) | 2017-07-31 | 2023-01-31 | Honda Motor Co., Ltd. | Continuous production of binder and collector-less self-standing electrodes for Li-ion batteries by using carbon nanotubes as an additive |
US11201318B2 (en) | 2017-09-15 | 2021-12-14 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
US11121358B2 (en) | 2017-09-15 | 2021-09-14 | Honda Motor Co., Ltd. | Method for embedding a battery tab attachment in a self-standing electrode without current collector or binder |
US11616221B2 (en) | 2017-09-15 | 2023-03-28 | Honda Motor Co., Ltd. | Method for battery tab attachment to a self-standing electrode |
US11489147B2 (en) | 2017-09-15 | 2022-11-01 | Honda Motor Co., Ltd. | Method for embedding a battery tab attachment in a self-standing electrode without current collector or binder |
EP3768784A4 (en) * | 2018-03-20 | 2021-12-22 | Graphite Innovation and Technologies Inc. | Multifunctional coatings for use in wet environments |
EP3591012A1 (en) * | 2018-07-05 | 2020-01-08 | Chung-Ping Lai | Conductive ink for use in manufacturing radio frequency identification (rfid) tag antenna and method for manufacturing rfid tag antenna |
US11719586B2 (en) | 2018-09-17 | 2023-08-08 | Goodrich Corporation | Additive manufactured strain gauge on component surfaces for predictive failure monitoring |
EP3629405A1 (en) * | 2018-09-27 | 2020-04-01 | Siemens Aktiengesellschaft | Lithium ion accumulator and material and method for producing the same |
EP3629402A1 (en) * | 2018-09-27 | 2020-04-01 | Siemens Aktiengesellschaft | Lithium-ion accumulator and material and method for manufacturing the same |
US10971281B2 (en) * | 2018-11-27 | 2021-04-06 | Global Graphene Group, Inc. | Conducting polymer composite containing ultra-low loading of graphene |
US20200168356A1 (en) * | 2018-11-27 | 2020-05-28 | Nanotek Instruments, Inc. | Conducting polymer composite containing ultra-low loading of graphene |
CN109852145A (en) * | 2018-12-28 | 2019-06-07 | 西安理工大学 | Biology base electrically conductive ink and its preparation method and application |
US11535517B2 (en) | 2019-01-24 | 2022-12-27 | Honda Motor Co., Ltd. | Method of making self-standing electrodes supported by carbon nanostructured filaments |
US11352258B2 (en) | 2019-03-04 | 2022-06-07 | Honda Motor Co., Ltd. | Multifunctional conductive wire and method of making |
US11325833B2 (en) | 2019-03-04 | 2022-05-10 | Honda Motor Co., Ltd. | Composite yarn and method of making a carbon nanotube composite yarn |
US11834335B2 (en) | 2019-03-04 | 2023-12-05 | Honda Motor Co., Ltd. | Article having multifunctional conductive wire |
CN110041761A (en) * | 2019-04-19 | 2019-07-23 | 电子科技大学中山学院 | Water-based conductive ink and preparation method thereof |
WO2020238144A1 (en) * | 2019-05-31 | 2020-12-03 | 厦门大学 | Plastic electroplating method |
CN110240831A (en) * | 2019-07-09 | 2019-09-17 | 兰州大学 | A kind of preparation method of graphene functional properties conductivity fabric |
US11539042B2 (en) | 2019-07-19 | 2022-12-27 | Honda Motor Co., Ltd. | Flexible packaging with embedded electrode and method of making |
CN111647322A (en) * | 2020-06-27 | 2020-09-11 | 德阳聪源光电科技股份有限公司 | Conductive ink composition for preparing flexible heating film |
CN111671163A (en) * | 2020-07-13 | 2020-09-18 | 诸暨初升新材料科技有限公司 | Preparation method of graphene heat-conducting ceramic heating body of electronic cigarette atomizer |
CN111849253A (en) * | 2020-08-07 | 2020-10-30 | 河南墨特石墨烯科技有限公司 | Graphene heating water-based ink and preparation method thereof |
CN112029342A (en) * | 2020-09-25 | 2020-12-04 | 欧菲微电子技术有限公司 | Conductive ink, ultrasonic fingerprint module and electronic equipment |
CN114621635A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Graphene-based battery electrode material screen printing conductive ink, and preparation method and application thereof |
CN112625508A (en) * | 2021-01-12 | 2021-04-09 | 陕西科技大学 | Preparation method of graphene conductive ink for 3D printing on paper |
WO2023147301A1 (en) * | 2022-01-28 | 2023-08-03 | Cabot Corporation | Conductive ink with carbon nanostructures |
US11962017B2 (en) | 2023-01-25 | 2024-04-16 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
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US20160360616A1 (en) | 2016-12-08 |
US11202369B2 (en) | 2021-12-14 |
US9456497B2 (en) | 2016-09-27 |
US20120007913A1 (en) | 2012-01-12 |
US20190380201A1 (en) | 2019-12-12 |
US10362673B2 (en) | 2019-07-23 |
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