CN106883684B - Graphene three-dimensional composite water-based electrothermal ink and preparation method thereof - Google Patents
Graphene three-dimensional composite water-based electrothermal ink and preparation method thereof Download PDFInfo
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Abstract
The invention provides a graphene three-dimensional composite water-based electrothermal ink and a preparation method thereof, wherein the graphene three-dimensional composite water-based electrothermal ink comprises a graphene dispersion liquid, a carbon nano tube dispersion liquid, a carbon black dispersion liquid, a first water-based resin and a first dispersing agent, so that the graphene, the carbon nano tube and the carbon black form a three-dimensional stable structure; the method for forming the three-dimensional nanostructure layer by adding the carbon black and the carbon nano tube between the graphene solves the problem that the electric heating conversion efficiency is attenuated due to the re-graphitization and graphitization of the electric heating film after the electric heating film is used for a long time; the carbon black is granular and can be regarded as zero-dimensional nano material; the carbon nano tube is in a line rod shape and belongs to a one-dimensional nano material; the graphene is flaky and is a two-dimensional nano material; the three materials are combined together to form a special three-dimensional carbon nano heating element in a lap joint manner; the single surface-to-surface contact of the skeleton network is changed into a point-to-point contact mode, a point-to-line contact mode, a line-to-surface contact mode and a surface-to-surface contact mode, so that the resistance stability of the skeleton network is improved while the conductive path is increased.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano composite materials, and relates to graphene three-dimensional composite water-based electrothermal ink and a preparation method thereof.
Background
The carbon-based conductive ink taking carbon black, graphite, carbon fiber and a mixture thereof as main fillers is widely applied to the fields of film switches, flexible circuits, medical electronics, communication equipment, electromagnetic shielding and the like except for electrothermal films due to the advantages of low cost, stable performance, high cost performance and the like. Inorganic nano-metal (such as copper series, silver series and the like) and organic (mostly conductive polymers) conductive ink have better conductivity, so that novel ink fillers such as nano conductive materials, polymer conductive materials and the like gradually replace the dominant research position of carbon series conductive fillers.
However, with the discovery and application of carbon nanomaterials such as carbon nanotubes and graphene, the novel carbon-based conductive ink prepared by using the carbon nanomaterials as a conductive agent has higher conductivity, better mechanical strength and lighter mass, and has good research and development prospects and market values. The traditional electrothermal film adopts conductive carbon black and graphite as conductive agents, the particle size is in the micron order, and the contact between the conductive agents is insufficient; in the long-term use of electrification, the amorphous carbon black vibrates for a long time under the action of an electric field to cause the contact structure between particles to be loosened, and the charge conduction route can generate irreversible negative change to cause power attenuation; the conductive ink using the graphene as the conductive agent is easy to agglomerate if the number of the graphene is increased, and the graphene is easily graphitized due to layer-by-layer superposition, so that the conductive path is reduced, the power attenuation is caused, and the service life of the traditional electrothermal film is limited.
Disclosure of Invention
Aiming at the problems, the invention provides the graphene three-dimensional composite water-based electrothermal ink with stable heating.
In order to achieve the purpose, the invention provides graphene three-dimensional composite water-based electrothermal ink which is characterized in that: the carbon black-based composite material comprises graphene, carbon nanotubes, carbon black, a first aqueous resin, a first dispersant and a second dispersant.
The invention relates to a graphene three-dimensional composite water-based electrothermal ink with stable heating, which is characterized in that graphene is firstly combined with a carbon nano tube and then arranged in a gap in a smart carbon black nano particle mode, so that the graphene, the carbon nano tube and carbon black form a three-dimensional stable structure, the problem of re-graphitization after long-time use of an electrothermal film is fundamentally solved, and the great problem of electric heating conversion efficiency attenuation caused by graphitization is solved. When the two electrodes are mutually fixed and mutually restricted, a large inlet and outlet space is created for free electrons, the graphitization effect of graphene during working is reduced, the resistance attenuation is relieved, the heating performance of the product is kept stable for a long time, and the problem of power attenuation of the like product after long-time use is solved.
Aiming at the problems, the invention provides a preparation method of graphene three-dimensional composite water-based electrothermal ink with stable heating.
In order to achieve the purpose, the invention discloses a preparation method of graphene three-dimensional composite water-based electrothermal ink, which is characterized by comprising the following specific steps:
preparing graphene ink liquid separation:
(1) taking 0.1-10 parts by weight of graphene powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.1-5 parts by weight of first dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(II) preparing multi-wall carbon nano tube ink liquid separation:
(1) taking 4-10 parts by weight of multi-wall carbon nanotube powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute under a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.5-2 parts by weight of second dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(III) preparing carbon black ink liquid separation:
(1) taking 0.1-10 parts by weight of carbon black powder, adding 90-120 parts by weight of purified water at the speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 46-50 hours;
(2) and cooling to normal temperature, filtering the liquid of the prepared carbon black ink, and filtering carbon black particles with the particle size of more than 30 nm.
And (IV) separating the graphene ink prepared in the step (I) and the multi-wall carbon nanotube ink prepared in the step (II) in a ratio of 1: 5 to obtain the graphene-carbon nanotube mixed solution.
And (V) separating the graphene-carbon nanotube mixed solution prepared in the step (IV) and the carbon black ink prepared in the step (III) to obtain the graphene three-dimensional composite water-based electrothermal ink.
Further, in the step (iv), the method includes the steps of:
(11) separating the graphene ink obtained in the step (one) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 1:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(12) separating the graphene-carbon nanotube mixed solution obtained in the step (11) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 2:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(13) separating the graphene-carbon nanotube mixed solution obtained in the step (12) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 3: 1, adding the first aqueous resin into the obtained mixed solution at the speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at the constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the constant temperature for 0.8-1.5 hours.
Further, in the step (five), the method comprises the steps of:
(21) mixing the graphene-carbon nanotube mixed solution obtained in the step (13) and the carbon black ink liquid obtained in the step (III) according to a ratio of 1:1, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(22) mixing the composite solution obtained in the step (21) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping rotating and stirring at 1500-2000rpm/min, and keeping the temperature constant for 0.8-1.5 hours;
(23) and (3) mixing the composite solution obtained in the step (22) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature for 0.8-1.5 hours.
Further, the first dispersion liquid in the step (one) is one or more of an organosilicone-modified polysiloxane dispersant, a sodium polycarboxylate dispersant, a copolymer dispersant containing pigment affinity groups, an organic ammonium polycarboxylate dispersant, a quaternary ammonium dispersant and a sulfonate dispersant.
Further, the second dispersion liquid in the step (III) is one or more of polymethacrylic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyethylene glycol p-isooctyl phenyl ether.
The invention relates to a preparation method of graphene three-dimensional composite water-based electrothermal ink, which is characterized in that graphene is firstly combined with a carbon nano tube and then arranged in a gap in a smart carbon black nano particle mode, so that the graphene, the carbon nano tube and carbon black form a three-dimensional stable structure, the structures are mutually fixed and mutually restricted, meanwhile, a large inlet and outlet space is created for free electrons, the graphitization effect existing during the working of the graphene is reduced, the resistance attenuation is relieved, the heating performance of a product is kept stable for a long time, and the problem of power attenuation of the similar product after long-time use is solved.
The reaction method does not need high reaction temperature, and can be used for preparing the product even at normal temperature, so that the reaction time is greatly reduced, the energy consumption is reduced, the preparation time is saved, the cost is saved, the efficiency is improved, and the profit is improved.
Drawings
FIG. 1 is a microscopic picture of the graphene three-dimensional composite aqueous electrothermal ink of the present invention;
FIG. 2 is a microscopic picture of the graphene three-dimensional composite aqueous electrothermal ink.
Detailed Description
The practice of particular embodiments of the present invention is further described below in conjunction with the appended drawings.
Example one
As shown in fig. 1-2, the graphene three-dimensional composite water-based electrothermal ink is characterized in that: the carbon black dispersion liquid comprises a graphene dispersion liquid, a carbon nano tube dispersion liquid, a carbon black dispersion liquid, a first water-based resin, a first dispersing agent and a second dispersing agent.
The graphene is firstly combined with the carbon nano tube and then arranged in the gap in a smart carbon black nano particle mode, so that the graphene, the carbon nano tube and the carbon black form a three-dimensional stable structure, the problem of graphitization after the electric heating film is used for a long time is fundamentally solved, and the great problem of electric heating conversion efficiency attenuation caused by graphitization is solved. The three materials form a skeleton network, and the mode of combining point contact, line contact and surface contact is changed from simple surface-to-surface contact, so that the stability of the resistance of the skeleton network is improved while the conductive path is increased. When the two electrodes are mutually fixed and mutually restricted, a large inlet and outlet space is created for free electrons, the graphitization effect of graphene during working is reduced, the resistance attenuation is relieved, the heating performance of the product is kept stable for a long time, and the problem of power attenuation of the like product after long-time use is solved.
The embodiment II discloses a preparation method of graphene three-dimensional composite water-based electrothermal ink, which is characterized by comprising the following specific steps of:
preparing graphene ink liquid separation:
(1) taking 0.1-10 parts by weight of graphene powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.1-5 parts by weight of first dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(II) preparing multi-wall carbon nano tube ink liquid separation:
(1) taking 4-10 parts by weight of multi-wall carbon nanotube powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute under a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.5-2 parts by weight of second dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(III) preparing carbon black ink liquid separation:
(1) taking 0.1-10 parts by weight of carbon black powder, adding 90-120 parts by weight of purified water at the speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 46-50 hours;
(2) and cooling to normal temperature, filtering the liquid of the prepared carbon black ink, and filtering carbon black particles with the particle size of more than 30 nm.
And (IV) separating the graphene ink prepared in the step (I) and the multi-wall carbon nanotube ink prepared in the step (II) in a ratio of 1: 5 to obtain the graphene-carbon nanotube mixed solution.
And (V) separating the graphene-carbon nanotube mixed solution prepared in the step (IV) and the carbon black ink prepared in the step (III) to obtain the graphene three-dimensional composite water-based electrothermal ink.
Through the combination of graphene and the carbon nano tube, the carbon black nano particles are arranged in the gap in an intelligent mode, so that the graphene, the carbon nano tube and the carbon black form a three-dimensional stable structure, the structure is mutually fixed and restricted, a large in-and-out space is created for free electrons, the graphitization effect of the graphene during working is reduced, the resistance attenuation is relieved, the heating performance of the product is kept stable for a long time, and the problem of power attenuation of the like product after long-time use is solved.
The reaction method does not need high reaction temperature, and can be used for preparing the product even at normal temperature, so that the reaction time is greatly reduced, the energy consumption is reduced, the preparation time is saved, the cost is saved, the efficiency is improved, and the profit is improved.
The most preferred first dispersant dose is 2.5%, and the most preferred first dispersant dose is 1.2%.
The preferred temperature is 50 ℃ to 70 ℃ and the most preferred temperature is 60 ℃. The most preferred reaction time is 48 hours.
In a third embodiment, on the basis of the above-mentioned embodiment, the step (fourth) includes the steps of:
(11) separating the graphene ink obtained in the step (one) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 1:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(12) separating the graphene-carbon nanotube mixed solution obtained in the step (11) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 2:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(13) separating the graphene-carbon nanotube mixed solution obtained in the step (12) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 3: 1, adding the first aqueous resin into the obtained mixed solution at the speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at the constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the constant temperature for 0.8-1.5 hours.
In a fourth embodiment, on the basis of the above embodiment, the step (v) includes the steps of:
(21) mixing the graphene-carbon nanotube mixed solution obtained in the step (13) and the carbon black ink liquid obtained in the step (III) according to a ratio of 1:1, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(22) mixing the composite solution obtained in the step (21) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping rotating and stirring at 1500-2000rpm/min, and keeping the temperature constant for 0.8-1.5 hours;
(23) and (3) mixing the composite solution obtained in the step (22) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature for 0.8-1.5 hours.
The preferred temperature is 50 ℃ to 70 ℃ and the most preferred temperature is 60 ℃. The most preferred reaction time is 1 hour.
Example five, in addition to the above examples, the first dispersion liquid in the step (a) is one or more of an organosilicone-modified polysiloxane dispersant, a polycarboxylate-based dispersant, a copolymer dispersant containing a pigment affinity group, an organic polycarboxylate-based dispersant, a quaternary ammonium-based dispersant, and a sulfonate-based dispersant.
Example six, on the basis of the above examples, the second dispersion liquid in the step (three) is one or more of polymethacrylic acid, cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, and polyethylene glycol p-isooctyl phenyl ether.
In the eighth embodiment, the reaction temperature in the step (132) is 25 to 100 ℃ and the reaction time is 46 to 50 hours, and the stirring is performed by using the downward rotation stirring.
The preferred temperature is 50 ℃ to 70 ℃ and the most preferred temperature is 60 ℃. The most preferred reaction time is 48 hours.
In an embodiment ninth, on the basis of the above embodiment, the step (2) includes the steps of:
(211) and (3) dispersing heat of the graphene dispersion liquid obtained in the step (112) and the carbon nano tube obtained in the step (122) according to a ratio of 1:1, adding the first aqueous resin into the obtained mixed solution, wherein the reaction temperature is 70-90 ℃, the stirring speed is 1500-2000rpm/min, and the high-speed rotation stirring is carried out, and the reaction time is 0.8-1.5 hours;
(212) dispersing the graphene-carbon nanotube mixed solution obtained in the step (211) and the carbon nanotubes obtained in the step (122) according to a ratio of 2:1, adding the first aqueous resin into the obtained mixed solution, wherein the reaction temperature is 70-90 ℃, the stirring speed is 1500-2000rpm/min, and the high-speed rotation stirring is carried out, and the reaction time is 0.8-1.5 hours;
(213) dispersing the graphene-carbon nanotube mixed solution obtained in the step (212) and the carbon nanotubes obtained in the step (122) according to a ratio of 3: 1, adding the first aqueous resin into the obtained mixed solution, wherein the reaction temperature is 70-90 ℃, the stirring speed is 1500-2000rpm/min, and the high-speed rotation stirring is carried out, and the reaction time is 0.8-1.5 hours.
The graphene dispersion liquid and the carbon nanotube dispersion liquid are mixed and added into the carbon nanotube dispersion liquid in a grading manner, so that the mixing is more sufficient, the carbon nanotube can be inserted between graphene sheet layers at a high speed, and the simple surface-to-surface contact is converted into the full linear-to-surface contact.
Tenth embodiment, on the basis of the above embodiments, the step (2) includes the steps of:
(311) mixing the graphene-carbon nanotube mixed solution obtained in the step (213) and the carbon black dispersion liquid obtained in the step (133) according to a ratio of 1:1, wherein the reaction temperature is 70-90 ℃, the stirring is 500-800rpm/min, and the medium-speed rotation stirring is carried out for 0.5-1.0 hour;
(312) mixing the composite solution obtained in the step (311) and the carbon black dispersion liquid obtained in the step (133) according to a ratio of 2:1, wherein the reaction temperature is 70-90 ℃, the stirring is 500-800rpm/min, and the medium-speed rotation stirring is carried out for 0.5-1.0 hour;
(313) and (3) mixing the composite solution obtained in the step (312) and the carbon black dispersion liquid obtained in the step (133) according to the ratio of 2:1, wherein the reaction temperature is 70-90 ℃, the stirring is 500-800rpm/min, and the medium-speed rotation stirring is carried out for 0.8-1.5 hours.
The carbon black dispersion liquid is added into the graphene-carbon nanotube mixed solution in a grading manner, so that the mixing is more sufficient, the carbon nanotubes can be inserted between graphene sheets at a high speed, and the simple surface-to-surface contact is changed into a mode of fully converting into point contact, point-to-point contact, line-to-surface contact and surface contact, so that the stability of the resistance of the framework network is improved while the conductive path is increased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (1)
1. A preparation method of graphene three-dimensional composite water-based electrothermal ink is characterized by comprising the following specific steps:
preparing graphene ink liquid separation:
(1) taking 0.1-10 parts by weight of graphene powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.1-5 parts by weight of first dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(II) preparing multi-wall carbon nano tube ink liquid separation:
(1) taking 4-10 parts by weight of multi-wall carbon nanotube powder, adding 90-120 parts by weight of purified water at a speed of 5-10 parts by weight/minute under a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 10 hours;
(2) adding 0.5-2 parts by weight of second dispersing agent at the speed of 0.1-1 part by weight/minute, heating to 25-100 ℃, keeping stirring downwards, and keeping the temperature constant for 46-50 hours;
(3) cooling to normal temperature and discharging;
(III) preparing carbon black ink liquid separation:
(1) taking 0.1-10 parts by weight of carbon black powder, adding 90-120 parts by weight of purified water at the speed of 5-10 parts by weight/minute in a stirring state, heating to 25-100 ℃ after adding, keeping stirring in a downward rotating mode, and keeping the temperature constant for 46-50 hours;
(2) cooling to normal temperature, filtering the liquid of the prepared carbon black ink, and filtering carbon black particles with the particle size of more than 30 nm;
mixing the graphene ink liquid separation prepared in the step (I) and the multi-wall carbon nanotube ink liquid separation prepared in the step (II) to obtain a graphene-carbon nanotube mixed solution;
fifthly, mixing the graphene-carbon nanotube mixed solution prepared in the step (four) and the carbon black ink prepared in the step (three) in a liquid separating manner to obtain graphene three-dimensional composite water-based electrothermal ink;
in the step (IV), the method comprises the following steps:
(11) separating the graphene ink obtained in the step (one) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 1:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(12) separating the graphene-carbon nanotube mixed solution obtained in the step (11) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 2:1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(13) separating the graphene-carbon nanotube mixed solution obtained in the step (12) and the multi-wall carbon nanotube ink obtained in the step (two) according to a ratio of 3: 1, adding a first aqueous resin into the obtained mixed solution at a speed of 5-10 parts by weight/min, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
in the step (V), the method comprises the following steps:
(21) mixing the graphene-carbon nanotube mixed solution obtained in the step (13) and the carbon black ink liquid obtained in the step (III) according to a ratio of 1:1, raising the temperature to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping 1500-2000rpm/min for rotary stirring, and keeping the temperature constant for 0.8-1.5 hours;
(22) mixing the composite solution obtained in the step (21) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping rotating and stirring at 1500-2000rpm/min, and keeping the temperature constant for 0.8-1.5 hours;
(23) mixing the composite solution obtained in the step (22) and the carbon black ink liquid obtained in the step (III) according to a ratio of 2:1, uniformly heating to 70-90 ℃ at a constant speed of 2-6 ℃/min, keeping rotating and stirring at 1500-2000rpm/min, and keeping the temperature constant for 0.8-1.5 hours;
the first dispersing agent in the step (one) is one or more of a sodium polycarboxylate dispersing agent, a copolymer dispersing agent containing pigment affinity groups, a quaternary ammonium dispersant and a sulfonate dispersing agent;
the second dispersing agent in the step (II) is one or more of polymethacrylic acid, hexadecyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and polyethylene glycol p-isooctyl phenyl ether.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275552A (en) * | 2013-05-20 | 2013-09-04 | Kmt纳米科技（香港）有限公司 | Carbon electric heating printing ink and preparation method thereof |
| CN105017831A (en) * | 2014-04-18 | 2015-11-04 | 新材料与产业技术北京研究院 | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint |
-
2017
- 2017-04-01 CN CN201710211519.8A patent/CN106883684B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275552A (en) * | 2013-05-20 | 2013-09-04 | Kmt纳米科技（香港）有限公司 | Carbon electric heating printing ink and preparation method thereof |
| CN105017831A (en) * | 2014-04-18 | 2015-11-04 | 新材料与产业技术北京研究院 | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint |
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