CN113683920A - High-temperature graphene conductive ink, microcrystalline plate and preparation method of microcrystalline plate - Google Patents
High-temperature graphene conductive ink, microcrystalline plate and preparation method of microcrystalline plate Download PDFInfo
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- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heater elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
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- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
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Abstract
The invention provides high-temperature graphene conductive ink, a microcrystalline plate and a preparation method thereof, belongs to the technical field of thermoelectric materials, and comprises the following steps: mixing graphene and absolute ethyl alcohol, and emulsifying to obtain an emulsion; ball-milling the emulsion; performing suction filtration on the ball-milled emulsion, and cleaning with deionized water to obtain neutral graphene; mixing a modifier, deionized water and the neutral graphene to obtain a mixed solution; and dispersing the mixed solution at the temperature of 30-50 ℃ to obtain the high-temperature graphene conductive ink. The high-temperature graphene conductive ink prepared by the preparation method of the high-temperature graphene conductive ink is good in high-temperature stability and strong in adhesive force, and the microcrystalline plate prepared by the preparation method of the microcrystalline plate is good in adhesive force and thermal stability and high in heat dissipation performance.
Description
Technical Field
The invention relates to the technical field of thermoelectric materials, in particular to high-temperature graphene conductive ink, a microcrystalline plate and a preparation method of the microcrystalline plate.
Background
The graphene conductive ink has the advantages of good conductivity, low cost, light weight and the like, and is widely applied to heating facilities such as electrothermal films and the like, and the fields of antistatic coatings, electromagnetic shielding and the like. In the field of microcrystalline plate heating, although the traditional electrothermal film is applied, the traditional electrothermal film is gradually replaced by the graphene conductive ink due to complex manufacturing process and low thermal efficiency, but most of the graphene conductive ink at the present stage adopts an oily solvent, so that the environment-friendly performance is insufficient, and the adhesive force is poor, the strength is low, and the high-temperature stability is poor.
Disclosure of Invention
The invention solves the problem of how to improve the adhesive force and the high-temperature stability of the graphene conductive ink.
In order to solve the above problems, the present invention provides a method for preparing a high temperature graphene conductive ink, comprising:
step S1, mixing graphene and absolute ethyl alcohol for emulsification to obtain an emulsion;
step S2, performing ball milling on the emulsion;
step S3, performing suction filtration on the emulsion subjected to ball milling in the step S2, and cleaning with deionized water to obtain neutral graphene;
step S4, mixing a modifier, deionized water and the neutral graphene obtained in the step S3 to obtain a mixed solution;
and step S5, dispersing the mixed solution at the temperature of 30-50 ℃ to obtain the high-temperature graphene conductive ink.
Further, the step S5 further includes: and grinding the dispersed mixed solution to obtain the high-temperature graphene conductive ink, wherein the particle size of the high-temperature graphene conductive ink is less than 20 microns.
Further, in the step S1, the mass ratio of the graphene to the absolute ethyl alcohol is 10: (1-5).
Further, in the step S1, the emulsifying time is 0.3h-1 h.
Further, in step S2, a ball mill tank is used for the ball milling, and a ratio of a mass of the milling bodies in the ball mill tank to a mass of the emulsion is 10: (1-5).
Further, in step S4, the modifier includes a binder, an aqueous leveling agent, an aqueous thickener, an aqueous dispersant and an aqueous defoamer, and the weight percentages of the neutral graphene, the binder, the aqueous leveling agent, the aqueous thickener, the aqueous dispersant, the aqueous defoamer and the deionized water in the mixed solution are 20 to 50 wt%, 10 to 30 wt%, 1 to 4 wt%, 0.1 to 3 wt%, 0.5 to 2 wt%, 0.1 to 2 wt% and 30 to 50 wt%, respectively.
Further, in the step S4, the dispersing time is 1h to 3 h.
Further, in step S1, the number of graphene layers is 3 to 5.
Compared with the prior art, the preparation method of the high-temperature graphene conductive ink has the advantages that the absolute ethyl alcohol and the graphene are fully contacted in the emulsification process through the emulsifying machine, so that the absolute ethyl alcohol is inserted into the sheet layer of the graphene, the graphene can be more fully stripped by the shearing force generated in the ball milling process, the graphene agglomeration in the ball milling process is prevented, the high-conductivity graphene is further obtained, meanwhile, the pH value of the graphene is adjusted by cleaning with deionized water in the suction filtration process, the temperature of mixed liquid in the dispersion process is controlled, the graphene with good dispersibility, high-temperature stability and high conductivity is obtained, and the further prepared high-temperature graphene aqueous conductive ink is good in high-temperature stability and strong in adhesive force.
The invention also provides a microcrystalline plate which comprises the high-temperature graphene conductive ink, wherein the high-temperature graphene conductive ink is prepared by the preparation method of the high-temperature graphene conductive ink.
Compared with the prior art, the microcrystalline plate and the preparation method of the high-temperature graphene conductive ink have the same advantages, and are not described herein again.
The invention also provides a preparation method of the microcrystalline plate, which is used for preparing the microcrystalline plate and comprises the following steps:
step T1, placing the high-temperature graphene conductive ink in a variable-frequency dispersion machine for dispersion for 20-40 min;
step T2, curing the high-temperature graphene conductive ink dispersed in the step T1 on a microcrystal board substrate in a screen printing or spraying mode;
step T3, placing the microcrystal plate substrate in the step T2 in a vacuum environment at 400-600 ℃ or N2Or sintering in inert gas for 7-15 min to obtain the microcrystal plate with the high-temperature graphene conductive ink.
Compared with the prior art, the preparation method of the microcrystalline board has the advantages that the microcrystalline board prepared by the preparation method of the microcrystalline board is dispersed by a variable frequency dispersing machine to obtain the high-temperature graphene conductive ink with good dispersibility and high conductivity, and then the high-temperature graphene conductive ink is solidified and sintered to obtain the microcrystalline board with good adhesive force, good thermal stability and high heat dissipation performance.
Drawings
Fig. 1 is a flowchart of a method for preparing a high-temperature graphene conductive ink according to an embodiment of the invention;
fig. 2 is a flowchart of a method for manufacturing a micro-crystal plate according to an embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a high-temperature graphene conductive ink, including:
step S1, mixing graphene and absolute ethyl alcohol for emulsification to obtain an emulsion;
step S2, performing ball milling on the emulsion;
step S3, performing suction filtration on the emulsion subjected to ball milling in the step S2, and cleaning with deionized water to obtain neutral graphene;
step S4, mixing a modifier, deionized water and the neutral graphene obtained in the step S3 to obtain a mixed solution;
and step S5, dispersing the mixed solution at the temperature of 30-50 ℃ to obtain the high-temperature graphene conductive ink.
According to the preparation method of the high-temperature graphene conductive ink, the absolute ethyl alcohol and the graphene are fully contacted in the emulsifying process through the emulsifying machine, so that the absolute ethyl alcohol is inserted into the sheet layer of the graphene, the graphene can be more fully stripped by shearing force generated in the ball milling process, the graphene is prevented from agglomerating in the ball milling process, the high-conductivity graphene is further obtained, meanwhile, deionized water is washed in the suction filtration process to adjust the pH value of the graphene, the temperature of mixed liquid in the dispersion process is controlled, the graphene with good dispersibility, high-temperature stability and high conductivity is obtained, and the further prepared high-temperature graphene water-based conductive ink is good in high-temperature stability and strong in adhesive force.
It should be noted that, the particle size of graphene is usually small, and the inter-layer structure forms very strong van der waals acting force due to the conjugated structure, so that the layers are very easy to stack and difficult to disperse, and therefore, in order to prevent the graphene from agglomerating, in the prior art, the operations of mixing the graphene with various modifiers, stirring, dispersing or the like are usually adopted, and the graphene is uniformly dispersed into the modifiers, but the effect is limited, and the phenomenon of intercalated graphene is usually not generated, whereas in the embodiment, the absolute ethyl alcohol and the graphene are put into the emulsifying machine for emulsification operation, and the gaps between immiscible molecules are broken by using the high-speed shearing force of the emulsifying machine, so that the absolute ethyl alcohol is inserted between the layers of the graphene, a three-dimensional mechanical network structure is built between the two-dimensional lamellar structures of the graphene, the van der waals acting force between graphene layers is effectively weakened, and the reinforcing effect is achieved for inhibiting agglomeration, and the absolute ethyl alcohol has excellent intercalation effect in the emulsification process, and is beneficial to improving the conductivity of the graphene. Meanwhile, Van der Waals acting force between graphene layers is weakened, the formed three-dimensional mechanical network structure is beneficial to fully stripping between the graphene layers in the later ball milling process, aggregation of the graphene after ball milling is effectively prevented, and the influence of the aggregation on the conductivity of the graphene is reduced.
Preferably, the step S5 further includes grinding the dispersed mixture to obtain the high-temperature graphene conductive ink, wherein the particle size of the high-temperature graphene conductive ink is less than 20 μm. In some embodiments, the preferred grinding mode is: and (3) measuring the particle size of the dispersed mixed solution, if the particle size is larger than 20 microns, placing the dispersed mixed solution in a three-roll grinder to grind for 15min-45min, measuring the particle size again, and if the particle size is still larger than 20 microns, repeating the grinding step until the particle size is smaller than 20 microns. In this process, a three-roll grinder can be used for grinding, and the rotation speed is preferably 500-. The particle size of the mixed solution can be detected by a laser particle size analyzer or a doctor blade particle size analyzer. When the particle size of the high-temperature graphene conductive ink is smaller than 20 microns, the conductivity is higher, when the high-temperature graphene conductive ink needs to be printed or sprayed, the high-temperature graphene conductive ink is strong in adhesive force and easy to print or spray, and when the high-temperature graphene conductive ink is combined with other materials, such as a microcrystalline board, the structural stability is good, and the appearance is attractive.
Preferably, in step S1, the mass ratio of graphene to absolute ethyl alcohol is 10: (1-5). When the mass ratio of the graphene to the absolute ethyl alcohol is in the range, the absolute ethyl alcohol is more favorably inserted between layers of the graphene, the structural stability of the graphene is improved, when the graphene is subjected to other shearing forces, the graphene can be fully stripped, the stripped graphene is prevented from being agglomerated, and the conductivity of the graphene is favorably improved.
Preferably, in step S1, the emulsifying time is 0.3h-1 h. After the graphene and the absolute ethyl alcohol are emulsified for 0.3h-1h by the emulsifying machine, the absolute ethyl alcohol is fully contacted with the graphene, and the absolute ethyl alcohol is intercalated into a sheet layer of the graphene, so that the graphene is prevented from being agglomerated in the subsequent treatment process, and further the conductivity is influenced.
Preferably, in step S2, the ball mill uses a ball mill tank, and the ratio of the mass of the milling bodies in the ball mill tank to the mass of the emulsion is 10: (1-5), the graphene is fully stripped and the particle size is reduced, wherein the rotating speed of the planetary ball milling tank is preferably 200-600 r/min.
Preferably, in step S4, the modifier includes a binder, an aqueous leveling agent, an aqueous thickener, an aqueous dispersant and an aqueous defoamer, and the neutral graphene, the binder, the aqueous leveling agent, the aqueous thickener, the aqueous dispersant, the aqueous defoamer and the deionized water account for 20-50 wt%, 10-30 wt%, 1-4 wt%, 0.1-3 wt%, 0.5-2 wt%, 0.1-2 wt% and 30-50 wt% of the mixed solution, respectively.
In some specific embodiments, the binder is selected from one or more of aqueous silicon fluoride resin, aqueous acrylic emulsion, aqueous polyurethane resin, aqueous polyurethane emulsion, aqueous epoxy resin and aqueous epoxy emulsion in a mass ratio of 1: 1; the aqueous leveling agent is selected from ionic polyacrylate; the aqueous thickening agent is selected from sodium polyacrylate; the water-based dispersant is selected from sodium methylene dinaphthalene sulfonate with the pH value of 7-9; the water-based defoaming agent is selected from silicon water treatment defoaming agents with the pH value of 6-8.
Therefore, the graphene material is modified by the aqueous environment-friendly modifier, so that the environment-friendly performance of the graphene conductive ink is improved, the use is safer, and the application range is wider. Due to the fact that the addition content of most of the modifiers is low, the influence on the conductivity of the graphene conductive ink can be reduced while the environment is protected.
Preferably, in step S4, the dispersing time is 1h-3 h. As can be seen from the above, the temperature of the mixed liquid is controlled within the range of 30 ℃ to 50 ℃ for dispersion in the dispersion process, and in order to ensure the temperature control in the dispersion process, the mixed liquid can be placed in a container with a water cooling device and then placed into a variable frequency dispersion machine for dispersion, the rotating speed of the variable frequency dispersion machine is controlled within 2000-5000r/min, and the dispersion time is controlled within 1h to 3h, so that the full dispersion of the mixed liquid is facilitated, the agglomeration is prevented, and the electrical conductivity is improved.
Preferably, in step S1, the number of graphene layers is 3 to 5, which is beneficial to inserting absolute ethyl alcohol between graphene layers during emulsification, and is beneficial to peeling graphene layers during ball milling, thereby improving ball milling efficiency.
The embodiment of the invention also provides a microcrystalline plate which comprises the high-temperature graphene conductive ink, wherein the high-temperature graphene conductive ink is prepared by the preparation method of the high-temperature graphene conductive ink in the embodiment.
The high-temperature graphene conductive ink contained in the microcrystalline plate provided by the embodiment of the invention has the advantages of good dispersibility and high-temperature stability, high conductivity and strong adhesive force, so that the obtained microcrystalline plate containing the high-temperature graphene conductive ink has the advantages of good high-temperature stability, high conductivity, stable structure, attractive appearance and high heat dissipation rate.
As shown in fig. 2, an embodiment of the present invention further provides a method for manufacturing a microcrystalline board, including:
step T1, placing the high-temperature graphene conductive ink in a variable-frequency dispersion machine for dispersion for 20-40 min; therefore, the high-temperature graphene conductive ink with good dispersibility is obtained, and the conductivity of the high-temperature graphene conductive ink is improved;
step T2, curing the high-temperature graphene conductive ink dispersed in the step T1 on a microcrystal board substrate in a screen printing or spraying mode; the method for curing the high-temperature graphene conductive ink by adopting the screen printing mode has the advantages of strong adaptability, thick ink layer, strong stereoscopic impression and light resistance, attractive appearance and large printing area; the spraying process is mature, and is also suitable for curing the high-temperature graphene conductive ink.
Step T3, placing the microcrystal plate substrate in the step T2 in a vacuum environment at 400-600 ℃ or N2Or sintering in inert gas for 7-15 min to obtain the microcrystal plate with the high-temperature graphene conductive ink. Thus, at elevated temperatures, vacuum or N is used2Or the inert gas isolates the high-temperature graphene conductive ink from the air, so that the high-temperature graphene conductive ink is prevented from reacting with the air at a high temperature and further undergoing qualitative change to influence the performance of the microcrystalline board.
The microcrystalline plate prepared by the preparation method of the microcrystalline plate in this embodiment is dispersed by a variable frequency dispersing machine to obtain the high-temperature graphene conductive ink with good dispersibility and high conductivity, and then the high-temperature graphene conductive ink is cured and sintered to obtain the microcrystalline plate with good adhesive force, good thermal stability and high heat dissipation performance.
Example 1
The preparation method of the high-temperature graphene conductive ink in the embodiment specifically comprises the following steps: adding a certain amount of graphene into an emulsifying machine, adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the graphene is 10:1, starting the emulsifying machine, and uniformly emulsifying for 0.3 h; the mixed solution is put into a planetary ball milling tank for ball milling for half an hour, and the ball-material ratio is 10: 1; and then placing the mixed solution on a vacuum suction filter, and washing the mixed solution for multiple times by using deionized water until the pH value of the filtrate is about 7. Respectively weighing 20 wt%, 30 wt%, 2.0 wt%, 1.5 wt%, 1.0 wt%, 0.5 wt% and 45 wt% of graphene, a binder, a water-based leveling agent, a water-based thickener, a water-based dispersant, a water-based defoamer and deionized water, blending the graphene, the binder, the water-based leveling agent, the water-based thickener, the water-based dispersant, the water-based defoamer and the deionized water in a double-layer stainless steel capacity cup with a water cooling device, placing the double-layer stainless steel capacity cup in a variable frequency dispersant for dispersing for 1 hour, and keeping the dispersion temperature of the mixed solution at 30 ℃. And detecting the particle size of the mixed product by using a laser particle sizer or a scraper particle sizer, if the particle size is larger than 20 microns, putting the mixed product into a three-roll grinder to grind for 15min, testing the particle size again, and repeating the steps until the particle size is smaller than 20 microns to prepare the high-temperature graphene conductive ink.
Example 2
In this embodiment, on the basis of embodiment 1, the high-temperature conductive ink obtained in embodiment 1 is placed in a variable frequency dispersion machine to be dispersed for 20min, and then is printed on a microcrystalline board substrate in a screen printing manner, or is sprayed on the microcrystalline board substrate by using a spraying process, and then the microcrystalline board substrate is placed in a vacuum environment at 400 ℃ or in an N environment2Or sintering in inert gas for 7min to obtain the microcrystal plate attached with the high-temperature graphene conductive ink.
Example 3
The preparation method of the high-temperature graphene conductive ink in the embodiment specifically comprises the following steps: adding a certain amount of graphene into an emulsifying machine, adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the graphene is 10:5, starting the emulsifying machine, and uniformly emulsifying for 1 h; and (3) putting the mixed solution into a planetary ball milling tank for ball milling for half an hour, wherein the ball-material ratio is 10: 5. The mixture was placed on a vacuum filtration machine and washed several times with deionized water until the pH of the filtrate was about 7. Respectively weighing 30 wt%, 20 wt%, 2.0 wt%, 1.5 wt%, 1.0 wt%, 0.5 wt% and 45 wt% of graphene, a binder, a water-based leveling agent, a water-based thickener, a water-based dispersant, a water-based defoamer and a solvent. The samples are blended in a double-layer stainless steel capacity cup with a water cooling device, placed in a variable frequency dispersing agent for dispersing for 3 hours, and the dispersion temperature of the mixed solution is kept at 50 ℃. And detecting the particle size of the mixed product by using a laser particle sizer or a scraper particle sizer, if the particle size is larger than 20 microns, putting the mixed product into a three-roll grinder to grind for 45min, testing the particle size again, and repeating the steps until the particle size is smaller than 20 microns to prepare the high-temperature graphene conductive ink.
Example 4
In this embodiment, on the basis of embodiment 3, the high-temperature graphene conductive ink obtained in embodiment 3 is placed in a variable frequency dispersion machine to be dispersed for 40min, and then is printed on a microcrystalline board substrate in a screen printing manner (or a spraying process), and then the microcrystalline board substrate is placed in a vacuum environment at 600 ℃ or in an N environment2Or sintering in inert gas for about 15min to obtain the microcrystal plate attached with the high-temperature graphene conductive ink.
Example 5
The preparation method of the high-temperature graphene conductive ink in the embodiment specifically comprises the following steps: adding a certain amount of graphene into an emulsifying machine, adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the graphene is 10:3, starting the emulsifying machine, and uniformly emulsifying for 0.6 h; and (3) putting the mixed solution into a planetary ball milling tank for ball milling for half an hour, wherein the ball-material ratio is 10: 2. The mixture was placed on a vacuum filtration machine and washed several times with deionized water until the pH of the filtrate was about 7. Respectively weighing 40 wt%, 10 wt%, 2.0 wt%, 1.5 wt%, 1.0 wt%, 0.5 wt% and 45 wt% of graphene, a binder, a water-based leveling agent, a water-based thickener, a water-based dispersant, a water-based defoamer and deionized water, blending the graphene, the binder, the water-based leveling agent, the water-based thickener, the water-based dispersant, the water-based defoamer and the deionized water in a double-layer stainless steel capacity cup with a water cooling device, placing the double-layer stainless steel capacity cup in a variable frequency dispersant for dispersing for 2 hours, and keeping the dispersion temperature of the mixed solution at 40 ℃. And detecting the particle size of the mixed product by using a laser particle sizer or a scraper particle sizer, if the particle size is larger than 20 microns, putting the mixed product into a three-roll grinder to grind for 25min, testing the particle size again, and repeating the steps until the particle size is smaller than 20 microns to prepare the high-temperature graphene conductive ink.
Example 6
In this embodiment, on the basis of embodiment 5, the high-temperature conductive ink obtained in embodiment 5 is placed in a variable frequency dispersion machine to be dispersed for 30min, and then is printed on a microcrystalline board substrate by a screen printing method (or a spraying process), and then the microcrystalline board substrate is placed in a vacuum environment of 500 ℃ or in an N environment2Or sintering in inert gas for about 10min to obtain the microcrystal plate attached with the high-temperature graphene conductive ink.
Example 7
The preparation method of the high-temperature graphene conductive ink in the embodiment specifically comprises the following steps: adding a certain amount of graphene into an emulsifying machine, adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the graphene is 10:1, starting the emulsifying machine, and uniformly emulsifying for 0.5 h; the mixed solution is put into a planetary ball milling tank for ball milling for half an hour, and the ball material ratio is 10: 2; and then placing the mixed solution on a vacuum suction filter, and washing the mixed solution for multiple times by using deionized water until the pH value of the filtrate is about 7. Respectively weighing 50 wt%, 10.5 wt%, 4.0 wt%, 3 wt%, 0.5 wt%, 2 wt% and 30 wt% of graphene, a binder, a water-based leveling agent, a water-based thickening agent, a water-based dispersing agent, a water-based defoaming agent and deionized water, blending the graphene, the binder, the water-based leveling agent, the water-based thickening agent, the water-based dispersing agent, the water-based defoaming agent and the deionized water in percentage by mass in a double-layer stainless steel capacity cup with a water cooling device, placing the double-layer stainless steel capacity cup in a variable frequency dispersing agent for dispersing for 1.5 hours, and keeping the dispersion temperature of the mixed solution at 38 ℃. And detecting the particle size of the mixed product by using a laser particle sizer or a scraper particle sizer, if the particle size is larger than 20 microns, putting the mixed product into a three-roll grinder to grind for 30min, testing the particle size again, and repeating the steps until the particle size is smaller than 20 microns to prepare the high-temperature graphene conductive ink.
Example 8
In this embodiment, on the basis of embodiment 7, the high-temperature conductive ink obtained in embodiment 7 is placed in a variable frequency dispersion machine to be dispersed for 28min, and then is printed on a microcrystalline substrate by a screen printing method, or is sprayed by a spraying processCoating the microcrystalline substrate on a microcrystalline substrate, and then placing the microcrystalline substrate in a vacuum environment at 450 ℃ or N2Or sintering in inert gas for 13min to obtain the microcrystal plate attached with the high-temperature graphene conductive ink.
Example 9
The preparation method of the high-temperature graphene conductive ink in the embodiment specifically comprises the following steps: adding a certain amount of graphene into an emulsifying machine, adding a proper amount of absolute ethyl alcohol, wherein the mass ratio of the absolute ethyl alcohol to the graphene is 10:1, starting the emulsifying machine, and uniformly emulsifying for 0.3 h; the mixed solution is put into a planetary ball milling tank for ball milling for half an hour, and the ball-material ratio is 10: 1; and then placing the mixed solution on a vacuum suction filter, and washing the mixed solution for multiple times by using deionized water until the pH value of the filtrate is about 7. Respectively weighing 30.8 wt%, 16 wt%, 1 wt%, 0.1 wt%, 2 wt%, 0.1 wt% and 50 wt% of graphene, a binder, a water-based leveling agent, a water-based thickening agent, a water-based dispersing agent, a water-based defoaming agent and deionized water, blending the graphene, the binder, the water-based leveling agent, the water-based thickening agent, the water-based dispersing agent, the water-based defoaming agent and the deionized water in percentage by mass in a double-layer stainless steel capacity cup with a water cooling device, placing the double-layer stainless steel capacity cup in a variable frequency dispersing agent for dispersing for 2.5 hours, and keeping the dispersion temperature of the mixed solution at 42 ℃. And detecting the particle size of the mixed product by using a laser particle sizer or a scraper particle sizer, if the particle size is larger than 20 microns, putting the mixed product into a three-roll grinder to grind for 40min, testing the particle size again, and repeating the steps until the particle size is smaller than 20 microns to prepare the high-temperature graphene conductive ink.
Example 10
In this embodiment, on the basis of embodiment 9, the high-temperature conductive ink obtained in embodiment 9 is placed in a variable frequency dispersion machine to be dispersed for 35min, and then is printed on the microlite substrate in a screen printing manner, or is sprayed on the microlite substrate by using a spraying process, and then the microlite substrate is placed in a 550 ℃ vacuum environment or in an N environment2Or sintering in inert gas for 9min to obtain the microcrystal plate attached with the high-temperature graphene conductive ink.
The above-described embodiments are only a part of embodiments, but not all embodiments of the present invention, and after the graphene high-temperature conductive ink in the above-described embodiments is printed or sprayed on a microcrystalline substrate and vacuum-sintered, each performance index of the test is as shown in table 1.
TABLE 1 high temperature graphene conductive ink Performance indices
The microcrystalline plate solidified with the graphene high-temperature conductive ink and prepared by the preparation method of the microcrystalline plate in the embodiment has the advantages of simple preparation process, short preparation period and good high-temperature stability, can ensure that the performance of the graphene high-temperature conductive ink is still stable and is not volatilized and layered when the surface of the microcrystalline plate is higher than 400 ℃ after the microcrystalline plate is connected with a circuit, has high hardness, can be seen from table 1, has the hardness of 3H and good adhesive force, and has the adhesive force grade detected by adopting a Baige test method reaching 1 grade or 2 grade.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A preparation method of high-temperature graphene conductive ink is characterized by comprising the following steps:
step S1, mixing graphene and absolute ethyl alcohol for emulsification to obtain an emulsion;
step S2, performing ball milling on the emulsion;
step S3, performing suction filtration on the emulsion subjected to ball milling in the step S2, and cleaning with deionized water to obtain neutral graphene;
step S4, mixing a modifier, deionized water and the neutral graphene obtained in the step S3 to obtain a mixed solution;
and step S5, dispersing the mixed solution at the temperature of 30-50 ℃ to obtain the high-temperature graphene conductive ink.
2. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein the step S5 further includes: and grinding the dispersed mixed solution to obtain the high-temperature graphene conductive ink, wherein the particle size of the high-temperature graphene conductive ink is less than 20 microns.
3. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein in the step S1, the mass ratio of the graphene to the absolute ethyl alcohol is 10: (1-5).
4. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein in the step S1, the emulsifying time is 0.3h-1 h.
5. The method for preparing the high-temperature graphene conductive ink according to claim 1, wherein in step S2, a ball mill pot is used for ball milling, and the ratio of the mass of the milling bodies in the ball mill pot to the mass of the emulsion is 10: (1-5).
6. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein in step S4, the modifier includes a binder, an aqueous leveling agent, an aqueous thickener, an aqueous dispersant and an aqueous defoamer, and the weight percentages of the neutral graphene, the binder, the aqueous leveling agent, the aqueous thickener, the aqueous dispersant, the aqueous defoamer and the deionized water in the mixed solution are 20-50 wt%, 10-30 wt%, 1-4 wt%, 0.1-3 wt%, 0.5-2 wt%, 0.1-2 wt% and 30-50 wt%, respectively.
7. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein in the step S4, the dispersing time is 1h-3 h.
8. The method for preparing a high-temperature graphene conductive ink according to claim 1, wherein in the step S1, the number of graphene layers is 3-5.
9. A microplate comprising a high-temperature graphene conductive ink, wherein the high-temperature graphene conductive ink is prepared by the preparation method of the high-temperature graphene conductive ink according to any one of claims 1 to 8.
10. A method for producing a microcrystal plate according to claim 9, which comprises:
step T1, placing the high-temperature graphene conductive ink in a variable-frequency dispersion machine for dispersion for 20-40 min;
step T2, curing the high-temperature graphene conductive ink dispersed in the step T1 on a microcrystal board substrate in a screen printing or spraying mode;
step T3, placing the microcrystal plate substrate in the step T2 in a vacuum environment at 400-600 ℃ or N2Or sintering in inert gas for 7-15 min to obtain the microcrystal plate with the high-temperature graphene conductive ink.
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| WO2023199210A1 (en) * | 2022-04-12 | 2023-10-19 | Graphenaton Technologies Sa | Ink comprising graphene |
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