CN113881287A - Water-based graphene conductive ink composition, water-based graphene conductive ink, and preparation method and application thereof - Google Patents
Water-based graphene conductive ink composition, water-based graphene conductive ink, and preparation method and application thereof Download PDFInfo
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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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
-
- 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
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- 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
-
- 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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
Abstract
The disclosure relates to a water-based graphene conductive ink composition, a water-based graphene conductive ink, and a preparation method and application thereof. The composition comprises a conductive unit, a connecting agent, an auxiliary agent and water; relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the conductive unit is 5-20 parts by weight, the content of the connecting agent is 20-25 parts by weight, the content of the auxiliary agent is 5-10 parts by weight, and the content of water is 45-70 parts by weight; wherein the conductive unit comprises graphene and modified conductive carbon black. The aqueous graphene conductive ink composition disclosed by the invention can be used for obtaining aqueous graphene conductive ink with low conductive unit content, good mechanical property and high conductivity, and is suitable for printed circuits, thin film switches, radio frequency identification, intelligent packaging and electromagnetic shielding.
Description
Technical Field
The disclosure relates to the technical field of printed electronic materials, in particular to a water-based graphene conductive ink composition, a water-based graphene conductive ink, and a preparation method and application thereof.
Background
The conductive ink is a composite conductive polymer material formed by adding conductive filler powder, such as carbon black, graphite, silver, copper and the like, into a polymer material, and is widely applied to printed circuit boards, membrane switches, REID radio frequency identification, printed resistors and the like. According to the different properties of the conductive filler, the conductive ink can be divided into gold conductive ink, silver conductive ink, copper conductive ink, carbon conductive ink and the like, and the gold conductive ink has excellent comprehensive performance but high price, and the application range is only limited to products with special requirements, such as thick film integrated circuits and the like. The conductivity of the silver conductive ink is second to that of gold powder, but the silver conductive ink is sensitive to temperature, has high temperature and strong conductivity, and is poor otherwise. The copper-based conductive ink is widely used and has high cost performance, but has the defect of easy oxidation. The carbon-based conductive ink is low in price, difficult to oxidize and stable in performance, but relatively poor in conductivity.
At present, conductive fillers used in carbon-based conductive inks mainly include conductive graphite, acetylene black, carbon nanotubes, graphene and the like, and are mainly applied to printed resistors and film switches. Graphene is a two-dimensional crystal consisting of carbon atoms only one layer of atomic thickness exfoliated from a graphite material. The connection between each carbon atom in graphene is very flexible, and when external mechanical force is applied, the surface of each carbon atom is bent and deformed, so that the carbon atoms do not need to be rearranged to adapt to external force, and the structure is kept stable. This stable lattice structure provides carbon atoms with excellent conductivity. The conductive ink prepared by taking the graphene as the conductive filler has good conductivity and printability, and has huge cost advantage compared with metal conductive ink, such as gold conductive ink, silver conductive ink, copper conductive ink and the like; compared with the traditional carbon-based conductive ink product, the graphene conductive ink has remarkable advantages in the aspect of conductivity.
The conductivity of the graphene conductive ink cannot meet the requirement due to interaction between graphene sheet layers in the conventional graphene conductive ink, and the graphene conductive ink has the defect of unstable performance. The main measure for improving the conductivity of the ink is to increase the content of the conductive agent, generally to 30-95 parts by weight, which can greatly improve the conductivity of the ink, but in the actual use process, because the content of the conductive agent is too high, the properties of the coating, such as workability, appearance quality, use stability and the like, are poor, the flexibility and adhesion of the coating are poor, and the phenomena of microcracks, falling and the like are easily generated, and the solvent-based ink contains a large amount of toxic and harmful volatile organic compounds, which seriously affects the human health and the environmental pollution.
Disclosure of Invention
The technical problem to be solved by the disclosure is how to reduce the content of a conductive agent and improve the conductivity of graphene conductive ink, and the aqueous graphene conductive ink composition, the aqueous graphene conductive ink, the preparation method and the application thereof are provided.
The first aspect of the present disclosure provides an aqueous graphene conductive ink composition, which includes a conductive unit, a linking agent, an auxiliary agent, and water; relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the conductive unit is 5-20 parts by weight, the content of the connecting agent is 20-25 parts by weight, the content of the auxiliary agent is 5-10 parts by weight, and the content of water is 45-70 parts by weight; wherein the conductive unit comprises graphene and modified conductive carbon black.
Optionally, the content of the conductive unit is 8-15 parts by weight, preferably 10-12 parts by weight, relative to 100 parts by weight of the aqueous graphene conductive ink composition;
the conductive unit further comprises conductive graphite powder, and the weight ratio of the graphene to the modified conductive carbon black to the conductive graphite powder is 1: (1-2): (0.5-1.5), wherein the weight ratio of the graphene to the modified conductive carbon black is 1: (1-4);
the graphene has an average particle size of 10-30 mu m, and the modified conductive carbon black has an average particle size of 5-25 mu m. The average particle size of the conductive graphite powder is 5-18 mu m.
Optionally, the modified conductive carbon black is a conductive carbon black subjected to surface oxidation modification by using an ammonium persulfate solution.
Optionally, the step of surface oxidation modification comprises: mixing an ammonium persulfate solution with conductive carbon black, and then carrying out ultrasonic treatment, stirring and drying to obtain the modified conductive carbon black;
the content of ammonium persulfate is 14-16 parts by weight, the content of water is 28-32 parts by weight, and the content of conductive carbon black is 1-5 parts by weight, relative to 100 parts by weight of the aqueous graphene conductive ink composition;
the conditions of the ultrasound include: the rated power of the ultrasonic equipment is 3000W, the working frequency is 20 +/-1 kHz, and the ultrasonic time is 2-4 h;
the stirring conditions include: the stirring speed is 500-1000rpm, and the stirring time is 12-48 h;
the drying conditions include: the drying temperature is 30-60 deg.C, and the drying time is 6-12 h.
Optionally, the linking agent is an aqueous polymer emulsion; the water-based polymer emulsion is selected from one or more of water-based acrylic emulsion, water-based polyurethane emulsion and water-based epoxy resin emulsion;
the auxiliary agent is selected from one or more of a defoaming agent, a leveling agent, a dispersing agent and a coupling agent;
relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the defoaming agent is 0.5-2 parts by weight, the content of the leveling agent is 0.5-1.5 parts by weight, the content of the dispersing agent is 3-6 parts by weight, and the content of the coupling agent is 0.5-1 part by weight;
the defoaming agent is selected from polydimethylsiloxane and/or polyether siloxane copolymer;
the leveling agent is selected from one or more of ionic acrylic acid copolymer, nonionic acrylic acid copolymer and polyether modified organic silicon;
the dispersing agent is selected from one or more of ammonium polyacrylate, sodium polyacrylate, potassium polyacrylate, sodium polycarboxylate, ammonium polycarboxylate, hydrophobically modified potassium polycarboxylate, self-emulsifying modified polyacrylate, fatty acid modified polyester, octylphenol polyoxyethylene ether, ethoxylated fatty acid and ethoxylated branched alcohol;
the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, phosphate coupling agent, borate coupling agent, bimetallic coupling agent and chromium complex.
A second aspect of the present disclosure provides a method for preparing an aqueous graphene conductive ink using the aqueous graphene conductive ink composition according to the first aspect of the present disclosure, the method including: and uniformly mixing the graphene, the modified conductive carbon black and the auxiliary agent, adding a connecting agent, and stirring to obtain the water-based graphene conductive ink.
Optionally, the method comprises the following steps:
(1) mixing the graphene, a dispersing agent and water, and performing ultrasonic dispersion until the particle size of D50 is smaller than 10 μm and the particle size of D90 is smaller than 15 μm to obtain a pretreated aqueous graphene dispersion liquid;
(2) mixing and stirring the aqueous graphene dispersion liquid, the modified conductive carbon black, the conductive graphite powder, the defoaming agent, the coupling agent and the dispersing agent to obtain a first mixture; grinding the first mixture until the D50 particle size is smaller than 5 μm and the D90 particle size is smaller than 10 μm, and filtering to obtain aqueous conductive slurry;
(3) mixing and stirring the aqueous conductive slurry, a connecting agent and a leveling agent to obtain aqueous graphene conductive ink;
wherein the modified conductive carbon black is obtained by performing surface oxidation modification on conductive carbon black by adopting an ammonium persulfate solution; the step of surface oxidation modification comprises: and mixing ammonium persulfate and water for dilution, adding conductive carbon black, performing ultrasonic treatment and stirring, and drying to obtain the modified conductive carbon black.
In a third aspect of the present disclosure, there is provided an aqueous graphene conductive ink prepared by the method according to the second aspect of the present disclosure.
Optionally, the sheet resistance of the aqueous graphene conductive ink is below 20 Ω.
A fourth aspect of the present disclosure provides a use of the aqueous graphene conductive graphite according to the third aspect of the present disclosure, where the use includes one or more of printed circuits, thin film switches, radio frequency identification, smart packaging, and electromagnetic shielding.
By the technical scheme, the aqueous graphene conductive ink composition can be used for obtaining aqueous graphene conductive ink with low conductive unit content, good mechanical property and high conductivity. The aqueous graphene conductive ink provided by the present disclosure can be used in printed circuits, membrane switches, radio frequency identification, smart packaging, and electromagnetic shielding. Meanwhile, water is used as a solvent, so that the environment-friendly and safe characteristics of environmental protection, no toxicity, no harm, no combustion, no explosion and the like are obvious.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the present disclosure provides an aqueous graphene conductive ink composition, which includes a conductive unit, a linking agent, an auxiliary agent, and water; relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the conductive unit is 5-20 parts by weight, the content of the connecting agent is 20-25 parts by weight, the content of the auxiliary agent is 5-10 parts by weight, and the content of water is 45-70 parts by weight; wherein the conductive unit comprises graphene and modified conductive carbon black.
According to the aqueous graphene conductive ink composition, graphene and modified conductive carbon black are used as conductive units, so that the conductive performance and the long-term stability of the aqueous graphene conductive ink are improved while the content of a conductive agent is reduced.
In one embodiment of the present disclosure, the content of the conductive unit is 8 to 15 parts by weight, preferably 10 to 12 parts by weight;
the conductive unit further comprises conductive graphite powder, and the weight ratio of the graphene to the modified conductive carbon black to the conductive graphite powder is 1: (1-2): (0.5-1.5), wherein the weight ratio of the graphene to the modified conductive carbon black is 1: (1-4);
the graphene has an average particle size of 10-30 mu m, and the modified conductive carbon black has an average particle size of 5-25 mu m. The average particle size of the conductive graphite powder is 5-18 mu m.
In the above embodiment, the conductive agent content of the conductive ink composition is further reduced, and the graphene, the modified conductive carbon black and the conductive graphite powder having a preferred particle size are used as the conductive unit, so that the workability, the appearance quality and the conductive performance of the conductive ink are improved, and the use stability is enhanced.
In one embodiment of the present disclosure, the modified conductive carbon black is a conductive carbon black that is surface-oxidatively modified with an ammonium persulfate solution.
In the embodiment, the performance influence caused by the graphene defect is compensated by the modified conductive carbon black, the conductive network structure is improved, and the conductive performance of the conductive ink is improved.
In one embodiment of the present disclosure, the step of surface oxidation modification comprises: mixing an ammonium persulfate solution with conductive carbon black, and then carrying out ultrasonic treatment, stirring and drying to obtain the modified conductive carbon black;
the content of ammonium persulfate is 14-16 parts by weight, the content of water is 28-32 parts by weight, and the content of conductive carbon black is 1-5 parts by weight, relative to 100 parts by weight of the aqueous graphene conductive ink composition;
the conditions of the ultrasound include: the rated power of the ultrasonic equipment is 3000W, the working frequency is 20 +/-1 kHz, and the ultrasonic time is 2-4 h;
the stirring conditions include: the stirring speed is 500-1000rpm, and the stirring time is 12-48 h;
the drying conditions include: the drying temperature is 30-60 deg.C, and the drying time is 6-12 h.
In the above embodiment, by preparing the modified conductive carbon black, the overall performance of the conductive ink is improved.
In one embodiment of the present disclosure, the linking agent is an aqueous polymer emulsion; the aqueous polymer emulsion can be selected from one or more of aqueous acrylic emulsion, aqueous polyurethane emulsion and aqueous epoxy resin emulsion;
the auxiliary agent is selected from one or more of a defoaming agent, a leveling agent, a dispersing agent and a coupling agent;
relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the defoaming agent is 0.5-2 parts by weight, the content of the leveling agent is 0.5-1.5 parts by weight, the content of the dispersing agent is 3-6 parts by weight, and the content of the coupling agent is 0.5-1 part by weight;
the antifoaming agent may be selected from polydimethylsiloxane and/or polyether siloxane copolymers;
the leveling agent can be selected from one or more of ionic acrylic acid copolymer, nonionic acrylic acid copolymer and polyether modified organic silicon;
the dispersing agent can be selected from one or more of ammonium polyacrylate, sodium polyacrylate, potassium polyacrylate, sodium polycarboxylate, ammonium polycarboxylate, hydrophobically modified potassium polycarboxylate, self-emulsifying modified polyacrylate, fatty acid modified polyester, octylphenol polyoxyethylene ether, ethoxylated fatty acid and ethoxylated branched alcohol;
the coupling agent can be one or more selected from silane coupling agent, titanate coupling agent, aluminate coupling agent, phosphate coupling agent, borate coupling agent, bimetallic coupling agent and chromium complex;
in the above embodiments, these additives can improve the conductivity, stability, surface properties of printed matter, printing adaptability, and the like of the ink, and improve the overall performance of the conductive ink.
A second aspect of the present disclosure provides a method for preparing an aqueous graphene conductive ink using the aqueous graphene conductive ink composition according to the first aspect of the present disclosure, the method including: and uniformly mixing the graphene, the modified conductive carbon black and the auxiliary agent, adding a connecting agent, and stirring to obtain the water-based graphene conductive ink.
In the embodiment, the aqueous graphene conductive ink with low conductive agent content, good mechanical property and high conductivity is prepared.
In one embodiment of the present disclosure, the method comprises the following steps:
(1) mixing the graphene, a dispersing agent and water, and performing ultrasonic dispersion until the particle size of D50 is smaller than 10 μm and the particle size of D90 is smaller than 15 μm to obtain a pretreated aqueous graphene dispersion liquid;
(2) mixing and stirring the aqueous graphene dispersion liquid, the modified conductive carbon black, the conductive graphite powder, the defoaming agent, the coupling agent and the dispersing agent to obtain a first mixture; grinding the first mixture until the D50 particle size is smaller than 5 μm and the D90 particle size is smaller than 10 μm, and filtering to obtain aqueous conductive slurry;
(3) mixing and stirring the aqueous conductive slurry, a connecting agent and a leveling agent to obtain aqueous graphene conductive ink;
wherein the modified conductive carbon black is obtained by performing surface oxidation modification on conductive carbon black by adopting an ammonium persulfate solution; the step of surface oxidation modification comprises: and mixing ammonium persulfate and water for dilution, adding conductive carbon black, performing ultrasonic treatment and stirring, and drying to obtain the modified conductive carbon black.
The preparation method disclosed by the invention is simple in steps and convenient to prepare, can obviously reduce the content of the conductive unit, and simultaneously keeps good mechanical property and high conductivity, so that the preparation process of the conductive ink is more economic, efficient, energy-saving and environment-friendly, and meanwhile, water is used as a solvent, so that the conductive ink has the obvious environmental protection and safety characteristics of environmental protection, no toxicity, no harm, no combustion, no explosion and the like.
The third aspect of the present disclosure provides an aqueous graphene conductive ink prepared by the method according to the second aspect of the present disclosure.
In a specific embodiment, the sheet resistance of the aqueous graphene conductive ink is below 20 Ω.
The fourth aspect of the present disclosure provides a use of the aqueous graphene conductive ink according to the third aspect of the present disclosure, and the use may include one or more of printed circuits, membrane switches, radio frequency identification, smart packaging, and electromagnetic shielding.
The method disclosed by the invention is simple in process, easy to industrialize, capable of obviously reducing the content of the conductive unit, and good in mechanical property and high in conductivity.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
In the following examples, the raw materials used were commercially available products unless otherwise specified.
The test methods employed in the following examples and comparative examples are as follows:
the D90 particle size and the average particle size (D50) were measured by a laser particle size distribution analyzer, the specific test method was: 2-5 drops of test sample are taken by a dropper and dropped into a sample measuring pool, stirring and ultrasonic dispersion are carried out, and the test is carried out after the dispersion is uniform.
The sheet resistance parameter of the conductive ink is tested by adopting an RTS-9 double-electric-measurement four-probe tester, and the specific test method comprises the following steps: coating conductive ink on a PET (Polyethylene terephthalate) substrate, completely drying and curing a coating film, wherein the dry film thickness of the coating film is 20-30 mu m, placing a sample on an operation table of a tester, pressing a probe by the operation table to enable the probe to be in contact with the surface of the coating film, switching on current, selecting a proper test range, and performing a coating film sheet resistance test after the current value is stabilized at a value specified by the tester;
the adhesion parameters are measured by GB 1720-89 paint film adhesion determination method;
the flexibility parameters were determined by GB/T1731-93 "paint film flexibility determination".
Example 1
Carrying out surface oxidation modification on conductive carbon black: adding 30 parts by weight of water into 15 parts by weight of ammonium persulfate to form an ammonium persulfate solution, adding 1 part by weight of conductive carbon black into the ammonium persulfate solution, performing ultrasonic treatment for 3 hours, performing magnetic stirring at 30 ℃ for 20 hours, performing centrifugal dispersion, and drying for 6 hours to obtain the modified conductive carbon black.
In this embodiment, the mass parts of the raw materials are: 3 parts of graphene (D50 ═ 17 μm), 3 parts of modified conductive carbon black (D50 ═ 8 μm), 2 parts of conductive graphite powder (D50 ═ 12 μm), 20 parts of an aqueous polyurethane emulsion, 3.2 parts of ammonium polyacrylate, 0.8 part of a silane coupling agent, 1 part of polyether-modified silicone, 1 part of a polyether siloxane copolymer, and 50 parts of water.
The invention provides high-conductivity aqueous graphene conductive ink which is prepared by the following steps:
(1) according to the weight, water and 2 parts of ammonium polyacrylate are stirred for 10min at the rotating speed of 500rpm at room temperature, then graphene is slowly added, and the mixture is stirred for 60min at the rotating speed of 1000 rpm; obtaining a mixture; placing the mixture into an energy-gathering ultrasonic dispersion machine for dispersion, wherein the rated power of ultrasonic equipment is 3000W, the working frequency is 20kHz, and the ultrasonic time is 8 hours until the particle size of D50 is less than 10 micrometers and the particle size of D90 is less than 15 micrometers, so as to obtain a pretreated aqueous graphene dispersion liquid;
(2) putting the pretreated aqueous graphene dispersion liquid into a high-speed dispersion grinder by weight, adding the polyether siloxane copolymer, the silane coupling agent and the residual ammonium polyacrylate at the rotating speed of 500rpm, then slowly adding the modified conductive carbon black and the conductive graphite powder, and stirring at the rotating speed of 1000rpm for 60min to obtain a mixture; grinding the mixture at a grinding speed of 3000rpm for 20h until the particle size of D50 is less than 5 μm and the particle size of D90 is less than 10 μm, and filtering and discharging to obtain aqueous conductive slurry;
(3) mixing the aqueous conductive slurry with the aqueous polyurethane emulsion and the polyether modified organic silicon by weight, and stirring at the rotating speed of 800rpm for 30min to obtain the aqueous graphene conductive ink.
Example 2
In this embodiment, the mass parts of the raw materials are: 3 parts of graphene, 4 parts of modified conductive carbon black, 4 parts of conductive graphite powder, 23 parts of aqueous acrylic emulsion, 4.2 parts of ammonium polyacrylate, 0.8 part of silane coupling agent, 1 part of ionic acrylic copolymer, 1 part of polydimethylsiloxane and 59 parts of water.
The procedure was as in example 1.
Example 3
In this embodiment, the mass parts of the raw materials are: 4 parts of graphene, 7 parts of modified conductive carbon black, 4 parts of conductive graphite powder, 25 parts of aqueous epoxy resin emulsion, 5 parts of ammonium polyacrylate, 0.8 part of silane coupling agent, 1 part of nonionic acrylic copolymer, 1 part of polydimethylsiloxane and 70 parts of water.
The procedure was as in example 1.
Example 4
The method of example 1 is used, with the only difference that: the graphene-modified carbon black composite material does not contain conductive graphite powder, 4 parts of graphene and 4 parts of modified conductive carbon black.
The procedure was as in example 1.
Example 5
The method of example 1 is used, with the only difference that: the average particle size of the graphene is 40 μm, the average particle size of the conductive carbon black is 30 μm, and the average particle size of the conductive graphite powder is 30 μm.
The procedure was as in example 1.
Example 6
The method of example 1 is used, with the only difference that: and (3) modifying the conductive carbon black by adopting sodium hypochlorite.
The procedure was as in example 1.
Comparative example 1
Compared with example 1, the difference is only that: and (3) a modification step without conductive carbon black, wherein the modified conductive carbon black is replaced by conductive carbon black with equal weight.
Comparative example 2
The raw materials and method of example 1 were used with the only difference that graphene was replaced with an equal weight of modified conductive carbon black.
Comparative example 3
The raw materials and method of example 1 were used except that the modified conductive carbon black was replaced with graphene of equal weight.
Test example
The aqueous graphene conductive inks obtained in the above examples and comparative examples are respectively coated on a substrate, dried and cured at room temperature, and then subjected to performance tests, wherein the dry film thickness of the coating film is 20-30 μm, and the test results are shown in the following table:
(poor dispersion means small particles in the coating, very poor dispersion means large particles in the coating)
As can be seen from the data in table 1, in examples 1 to 6, the graphene and the modified conductive carbon black are used as the conductive unit, so that the aqueous graphene conductive ink with low conductive unit content, good mechanical properties and high conductivity can be obtained, and can be used for printed circuits, thin film switches, radio frequency identification, intelligent packaging and electromagnetic shielding. The aqueous graphene conductive ink provided by the comparative examples 1-3 is large in sheet resistance, poor in conductivity, extremely poor in dispersibility and large in particle size. Therefore, the performance of the aqueous graphene conductive ink provided in the embodiments 1 to 6 of the present disclosure is more excellent than that of the comparative examples 1 to 3.
Comparing the data of example 1 and example 4, it can be seen that the preferred weight ratio of graphene, modified conductive carbon black and conductive graphite powder in the present disclosure is 1: (1-2): (0.5-1.5), the aqueous graphene conductive ink prepared by the method disclosed by the invention is low in conductive sheet resistance and better in conductive performance; comparing the data of example 1 and example 5, it can be seen that when the average particle size of the graphene preferred in the present disclosure is 10-30 μm, the average particle size of the modified conductive carbon black is 5-25 μm, and the average particle size of the conductive graphite powder is 5-18 μm, the conductivity of the aqueous graphene conductive ink prepared by the method of the present disclosure is better; comparing the data of example 1 and example 6, it can be seen that the sheet resistance of the aqueous graphene conductive ink prepared by the method of the present disclosure is smaller and the appearance and flexibility properties are better when the ammonium persulfate solution is preferably used as a modifier of the conductive carbon black in the present disclosure.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (10)
1. An aqueous graphene conductive ink composition, characterized in that the composition comprises a conductive unit, a linking agent, an auxiliary agent and water; relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the conductive unit is 5-20 parts by weight, the content of the connecting agent is 20-25 parts by weight, the content of the auxiliary agent is 5-10 parts by weight, and the content of water is 45-70 parts by weight; wherein the conductive unit comprises graphene and modified conductive carbon black.
2. The aqueous graphene conductive ink composition according to claim 1, wherein the conductive unit is contained in an amount of 8 to 15 parts by weight, preferably 10 to 12 parts by weight, with respect to 100 parts by weight of the aqueous graphene conductive ink composition;
the conductive unit further comprises conductive graphite powder, and the weight ratio of the graphene to the modified conductive carbon black to the conductive graphite powder is 1: (1-2): (0.5-1.5), wherein the weight ratio of the graphene to the modified conductive carbon black is 1: (1-4);
the graphene has an average particle size of 10-30 mu m, and the modified conductive carbon black has an average particle size of 5-25 mu m. The average particle size of the conductive graphite powder is 5-18 mu m.
3. The aqueous graphene conductive ink composition according to claim 1, wherein the modified conductive carbon black is a conductive carbon black surface-modified by oxidation using an ammonium persulfate solution.
4. The aqueous graphene conductive ink composition according to claim 3, wherein the surface oxidation modification step comprises: mixing an ammonium persulfate solution with conductive carbon black, and then carrying out ultrasonic treatment, stirring and drying to obtain the modified conductive carbon black;
the content of ammonium persulfate is 14-16 parts by weight, the content of water is 28-32 parts by weight, and the content of conductive carbon black is 1-5 parts by weight, relative to 100 parts by weight of the aqueous graphene conductive ink composition;
the conditions of the ultrasound include: the rated power of the ultrasonic equipment is 3000W, the working frequency is 20 +/-1 kHz, and the ultrasonic time is 2-4 h;
the stirring conditions include: the stirring speed is 500-1000rpm, and the stirring time is 12-48 h;
the drying conditions include: the drying temperature is 30-60 deg.C, and the drying time is 6-12 h.
5. The aqueous graphene conductive ink composition according to claim 1, wherein the linking agent is an aqueous polymer emulsion; the water-based polymer emulsion is selected from one or more of water-based acrylic emulsion, water-based polyurethane emulsion and water-based epoxy resin emulsion;
the auxiliary agent is selected from one or more of a defoaming agent, a leveling agent, a dispersing agent and a coupling agent;
relative to 100 parts by weight of the aqueous graphene conductive ink composition, the content of the defoaming agent is 0.5-2 parts by weight, the content of the leveling agent is 0.5-1.5 parts by weight, the content of the dispersing agent is 3-6 parts by weight, and the content of the coupling agent is 0.5-1 part by weight;
the defoaming agent is selected from polydimethylsiloxane and/or polyether siloxane copolymer;
the leveling agent is selected from one or more of ionic acrylic acid copolymer, nonionic acrylic acid copolymer and polyether modified organic silicon;
the dispersing agent is selected from one or more of ammonium polyacrylate, sodium polyacrylate, potassium polyacrylate, sodium polycarboxylate, ammonium polycarboxylate, hydrophobically modified potassium polycarboxylate, self-emulsifying modified polyacrylate, fatty acid modified polyester, octylphenol polyoxyethylene ether, ethoxylated fatty acid and ethoxylated branched alcohol;
the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, phosphate coupling agent, borate coupling agent, bimetallic coupling agent and chromium complex.
6. A method for preparing an aqueous graphene conductive ink by using the aqueous graphene conductive ink composition according to any one of claims 1 to 5, the method comprising: and uniformly mixing the graphene, the modified conductive carbon black and the auxiliary agent, adding a connecting agent, and stirring to obtain the water-based graphene conductive ink.
7. Method according to claim 6, characterized in that it comprises the following steps:
(1) mixing the graphene, a dispersing agent and water, and performing ultrasonic dispersion until the particle size of D50 is smaller than 10 μm and the particle size of D90 is smaller than 15 μm to obtain a pretreated aqueous graphene dispersion liquid;
(2) mixing and stirring the aqueous graphene dispersion liquid, the modified conductive carbon black, the conductive graphite powder, the defoaming agent, the coupling agent and the dispersing agent to obtain a first mixture; grinding the first mixture until the D50 particle size is smaller than 5 μm and the D90 particle size is smaller than 10 μm, and filtering to obtain aqueous conductive slurry;
(3) mixing and stirring the aqueous conductive slurry, a connecting agent and a leveling agent to obtain aqueous graphene conductive ink;
wherein the modified conductive carbon black is obtained by performing surface oxidation modification on conductive carbon black by adopting an ammonium persulfate solution; the step of surface oxidation modification comprises: and mixing ammonium persulfate and water for dilution, adding conductive carbon black, performing ultrasonic treatment and stirring, and drying to obtain the modified conductive carbon black.
8. An aqueous graphene conductive ink, characterized by being prepared by the method of any one of claims 6 to 7.
9. The aqueous graphene conductive ink according to claim 8, wherein the sheet resistance of the aqueous graphene conductive ink is less than 20 Ω.
10. Use of the aqueous graphene conductive graphite of claim 9, comprising one or more of printed circuits, thin film switches, radio frequency identification, smart packaging, and electromagnetic shielding.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558378A (en) * | 2022-10-31 | 2023-01-03 | 上海席亚高分子材料有限公司 | Ultrathin coating conductive coating and preparation method thereof |
| CN116515346A (en) * | 2023-04-18 | 2023-08-01 | 甘肃旭碳新材料有限公司 | Water-based graphene conductive ink and preparation method and application thereof |
| CN117089242A (en) * | 2023-10-19 | 2023-11-21 | 琥崧科技集团股份有限公司 | Preparation method of ink and ink |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337639A (en) * | 2013-06-24 | 2013-10-02 | 太原理工大学 | Preparation method of carbon nano tube array/carbon fiber fabric integrated three-dimensional porous air electrode |
| CN106752385A (en) * | 2017-01-11 | 2017-05-31 | 青岛瑞利特新材料科技有限公司 | A kind of Graphene modified water-soluble electrically conductive ink and preparation method thereof |
| CN107903713A (en) * | 2017-11-29 | 2018-04-13 | 北京旭碳新材料科技有限公司 | Highly conductive watersoluble plumbago alkene electrically conductive ink and preparation method thereof, composition |
| CN108570265A (en) * | 2018-06-12 | 2018-09-25 | 苏州中亚油墨有限公司 | A kind of aqueous composite conducting ink and preparation method thereof |
| WO2018228407A1 (en) * | 2017-06-14 | 2018-12-20 | 厦门信达光电物联科技研究院有限公司 | Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof |
-
2021
- 2021-10-21 CN CN202111229585.0A patent/CN113881287A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337639A (en) * | 2013-06-24 | 2013-10-02 | 太原理工大学 | Preparation method of carbon nano tube array/carbon fiber fabric integrated three-dimensional porous air electrode |
| CN106752385A (en) * | 2017-01-11 | 2017-05-31 | 青岛瑞利特新材料科技有限公司 | A kind of Graphene modified water-soluble electrically conductive ink and preparation method thereof |
| WO2018228407A1 (en) * | 2017-06-14 | 2018-12-20 | 厦门信达光电物联科技研究院有限公司 | Graphene/metal nanobelt composite conductive ink, preparation method therefor and application thereof |
| CN107903713A (en) * | 2017-11-29 | 2018-04-13 | 北京旭碳新材料科技有限公司 | Highly conductive watersoluble plumbago alkene electrically conductive ink and preparation method thereof, composition |
| CN108570265A (en) * | 2018-06-12 | 2018-09-25 | 苏州中亚油墨有限公司 | A kind of aqueous composite conducting ink and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王文广: "《聚合物改性原理》" * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558378A (en) * | 2022-10-31 | 2023-01-03 | 上海席亚高分子材料有限公司 | Ultrathin coating conductive coating and preparation method thereof |
| CN116515346A (en) * | 2023-04-18 | 2023-08-01 | 甘肃旭碳新材料有限公司 | Water-based graphene conductive ink and preparation method and application thereof |
| CN117089242A (en) * | 2023-10-19 | 2023-11-21 | 琥崧科技集团股份有限公司 | Preparation method of ink and ink |
| CN117089242B (en) * | 2023-10-19 | 2024-01-02 | 琥崧科技集团股份有限公司 | Preparation method of ink and ink |
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