CN109749519B - Composite graphene floor heating slurry and preparation method thereof - Google Patents
Composite graphene floor heating slurry and preparation method thereof Download PDFInfo
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- CN109749519B CN109749519B CN201910098201.2A CN201910098201A CN109749519B CN 109749519 B CN109749519 B CN 109749519B CN 201910098201 A CN201910098201 A CN 201910098201A CN 109749519 B CN109749519 B CN 109749519B
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Abstract
The invention belongs to the technical field of floor heating slurry, and particularly relates to composite graphene floor heating slurry and a preparation method thereof; the composite graphene floor heating slurry comprises the following components in parts by weight: 0.1-30 parts of carbon fiber/graphene/carbon microsphere powder, 0.1-70 parts of matrix binder, 0.1-5 parts of dispersing agent, 0.1-5 parts of flatting agent, 0.1-5 parts of anti-settling agent and 0.1-1 part of defoaming agent. The composite graphene floor heating slurry prepared from the carbon fiber/graphene/carbon microsphere composite powder has the characteristics of good adhesion, high conductivity, water resistance, alcohol resistance and the like; also has excellent conductive uniformity and anti-attenuation property.
Description
Technical Field
The invention belongs to the technical field of floor heating slurry, and particularly relates to composite graphene floor heating slurry and a preparation method thereof.
Background
With the vigorous popularization of the winter heating policy, more and more researchers are focusing on the development and application of carbon material conductive ink printing electric heating products, which are based on the fact that carbon materials have excellent electric conduction and heat transfer properties. The floor heating electric heating film prepared by printing is widely applied to northern heating; the heating element is prepared by modifying short carbon fibers, performing ball milling treatment to prepare microcrystal particles, adding a far infrared emitting agent, and synthesizing by a special process, and has the working principle that under the excitation caused by electricity, carbon molecular groups generate Brownian motion, and the carbon molecules collide and rub with each other to generate heat energy and generate a large amount of infrared radiation, wherein the conversion rate of electric energy and heat energy reaches more than 98%; however, the electrothermal film made of the existing carbon crystal electrothermal ink has the defect of power attenuation, so that the service life of the film product is short, and the later maintenance cost is increased.
Disclosure of Invention
Based on the defects in the prior art, the invention provides the composite graphene floor heating slurry and the preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite graphene floor heating slurry comprises the following components in parts by weight: 0.1-30 parts of carbon fiber/graphene/carbon microsphere powder, 0.1-70 parts of matrix binder, 0.1-5 parts of dispersing agent, 0.1-5 parts of flatting agent, 0.1-5 parts of anti-settling agent and 0.1-1 part of defoaming agent.
Preferably, the carbon fiber/graphene/carbon microsphere powder is prepared by growing graphene on the surfaces of carbon fibers and carbon microspheres through vapor deposition.
Preferably, the matrix binder is polyurethane and/or epoxy resin with the molecular weight of 50000-100000, and the anti-precipitation agent is fumed silica; the sheet resistance of the composite graphene floor heating slurry is 40-4000 omega/□, the viscosity is 3000-30000 cps, and the granularity is 5-10 mu m.
The invention also provides a preparation method of the composite graphene floor heating slurry, which comprises the following steps:
(1) preparing carbon fiber/graphene/carbon microsphere powder;
(2) mixing carbon fiber/graphene/carbon microsphere powder, matrix binder, dispersant, flatting agent, anti-settling agent and defoaming agent according to a preset proportion, grinding and stirring to obtain the composite graphene floor heating slurry.
Preferably, the step (1) comprises the following steps:
(11) cutting the pre-oxidized carbon fiber precursor into short fibers with target length; taking coal pitch as a raw material, generating a carbon microsphere mixture in a reaction kettle by adopting a medium-temperature thermal polymerization method, and separating and extracting by using an organic solvent to obtain carbon microsphere powder;
(12) mechanically dispersing short fiber and carbon microsphere powder in an organic solvent II, adding ferric nitrate nonahydrate, mechanically mixing, drying to obtain powder, transferring to an alumina crucible for high-temperature carbonization, carrying out vapor deposition on graphene in a high-temperature vapor deposition furnace to obtain carbon fiber/graphene/carbon microsphere powder, and finally collecting the carbon fiber/vapor carbon tube composite powder through a powder collector.
Preferably, the specification of the pre-oxidized carbon fiber precursor is 1-12K; the length of the short fiber is 1-6 mm; the coal pitch is medium-temperature coal pitch; the organic solvent I is toluene and n-hexane; the reaction conditions of the medium-temperature thermal polymerization method are as follows: the temperature is 300-400 ℃, the stirring speed is 100-700 r/min, the pressure is 1.0MPa, and the time is 0.1-8 h.
As a preferred scheme, the specification of the pre-oxidized carbon fiber precursor is 1-3K; the length of the short fiber is 1-3 mm.
Preferably, the mechanical dispersing in the step (12) is performed by a ball mill, a sand mill or a bluemill; when the mechanical dispersion mode is a ball mill, the ball milling medium is zirconia balls with the diameter of 1-3 mm, the ball milling time is 0.1-4 h, the ball milling temperature is controlled to be 20-30 ℃, the particle size of carbon fiber precursor powder obtained by ball milling is not more than 20 microns, and the particle size of carbon microsphere powder is 5-15 microns; the organic solvent II is one or more of glycol, ethanol and glycerol; the drying mode is freeze drying, vacuum drying or heating blast drying; the mass ratio of the carbon fiber precursor powder to the carbon microsphere powder to the organic solvent II to the ferric nitrate nonahydrate is (0.1-1): 0.1-1: 0.1-1: 0.1 to 1.
Preferably, the vapor deposition conditions are as follows: in a high-temperature vapor deposition furnace, methane and hydrogen are used as gas sources, nitrogen is used as a protective gas source, and the temperature is 800-1200 ℃.
Preferably, the mass ratio of the methane to the hydrogen is 0.1-8: 1.
compared with the prior art, the invention has the beneficial effects that:
the floor heating slurry prepared from the carbon fiber/graphene/carbon microsphere composite powder has the characteristics of good adhesion, high conductivity, water resistance, alcohol resistance and the like; also has excellent conductive uniformity and anti-attenuation property.
The preparation method of the invention has simple process and easy operation, and also has the following advantages:
(1) the invention adopts a physical method to prepare micron-sized carbon fiber powder, and asphalt is used for preparing carbon microspheres; taking micron-sized carbon fiber powder and carbon microspheres as a graphene carrier substrate, and grinding and mixing ferric nitrate nonahydrate to the inner surface of the fiber to provide a growth point for the composite graphene; and (3) carrying out catalytic pyrolysis on methane and hydrogen to grow graphene, and carrying out high-temperature carbonization to prepare the carbon fiber/graphitized carbon microsphere/graphene composite powder.
(2) And filling carbon fiber/graphene/carbon microsphere composite powder serving as conductive filler into resin to obtain the floor heating slurry with uniform resistance.
(3) The carbon microspheres are used as point-shaped particles and are uniformly dispersed in the organic filler, and the carbon fiber/graphene composite carbon microspheres are anchored in the resin, so that the floor heating slurry can be stored for a long time without deterioration; the printed electric heating coating has even resistance and the film layer generates heat evenly.
(4) The heating product prepared from the ground heating slurry improves the resistance uniformity, prolongs the service life and the like.
Drawings
Fig. 1 is a flowchart of a preparation method of the composite graphene floor heating slurry according to the first embodiment of the invention.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
The first embodiment is as follows:
as shown in fig. 1, the preparation method of the composite graphene floor heating slurry in the embodiment includes the following steps:
preparation of preoxidized carbon fiber short fiber and carbon microsphere
(1) Pre-oxidized carbon fiber precursor (2kg) with the specification of 3K is placed into a disc extrusion type fiber cutting machine (3kW power), and the pre-oxidized carbon fiber precursor is cut into short fibers with the length of 3 mm.
(2) Preparing carbon microspheres by adopting a medium-temperature thermal polymerization method: taking medium-temperature coal pitch, putting the medium-temperature coal pitch into a pressurized and sealed reaction kettle, heating the pressure to be 1.0MPa and the temperature to be 350 ℃, stirring at the speed of 400r/min for 4 hours to obtain a carbon microsphere mixture, and extracting organic solvents of toluene and n-hexane to obtain carbon microspheres; drying and washing with ethanol to obtain the carbon microsphere with the particle size of 10 microns.
Preparation of carbon fiber/graphene/carbon microsphere composite powder
Pre-oxidized 3kg of carbon fiber short fiber and 2kg of carbon microsphere powder are added with 2kg of ferric nitrate nonahydrate and 50L of ethanol organic solvent, the diameter is 1mGrinding m zirconia balls for 0.5h, and controlling the ball milling temperature to be 20-30 ℃; ball-milling and drying to obtain a mixture of carbon fiber precursor powder with the particle size of 10-20 microns, carbon microspheres with the particle size of 5-10 microns and ferric nitrate nonahydrate; placing in an alumina crucible, transferring into a high temperature vapor deposition furnace, introducing nitrogen N for 5 min2For discharging air inside the tube; then the temperature is increased to 450 ℃ (the temperature increase rate is 20 ℃/min); keeping for half an hour, heating to 950 deg.C, and introducing methane and hydrogen H2(methane with Hydrogen H)2The mass ratio of (1): 4) preparing graphene through high-temperature deposition; wherein the nitrogen flow is always kept at 100sccm until the reaction is finished; methane and hydrogen H are turned off2Thereafter, the nitrogen N may be turned off2(ii) a And finally, collecting carbon fiber/graphene/carbon microsphere powder through a powder collector.
Preparation of composite graphene floor heating slurry
Taking 20 parts of carbon fiber/graphene/carbon microsphere powder, 60 parts of matrix binder (containing curing agent), 5 parts of dispersing aid BYK-190, 5 parts of leveling aid BYK-333, 4.5 parts of anti-precipitant fumed silica, 0.5 part of defoaming agent KS-66 and the like, sequentially adding the materials into a stirring cylinder, uniformly stirring, and grinding by a three-roller machine until the discharge granularity is 5-10 mu m; the grinding temperature is 25-35 ℃, and the composite graphene floor heating slurry can be obtained, wherein the sheet resistance of the composite graphene floor heating slurry is 60-80 omega/□, and the viscosity is 10000-13000 cps. Wherein, the matrix binder is polyurethane and/or epoxy resin with the molecular weight of 50000-100000.
Example two:
the difference between the present embodiment and the first embodiment is: the particle size of the carbon fiber precursor powder is different from that of the carbon microsphere.
The preparation method of the composite graphene floor heating slurry comprises the following steps:
preparation of preoxidized carbon fiber short fiber and carbon microsphere
(1) Pre-oxidized carbon fiber precursor (2kg) with the specification of 3K is placed into a disc extrusion type fiber cutting machine (3kW power), and the pre-oxidized carbon fiber precursor is cut into short fibers with the length of 3 mm.
(2) Preparing carbon microspheres by adopting a medium-temperature thermal polymerization method: taking medium-temperature coal pitch, putting the medium-temperature coal pitch into a pressurized and sealed reaction kettle, heating the pressure to be 1.0MPa and the temperature to be 390 ℃, stirring the mixture at a speed of 500r/min for 4 hours to obtain a carbon microsphere mixture, and extracting organic solvents toluene and n-hexane to obtain carbon microspheres; drying and washing with ethanol to obtain the carbon microsphere with the particle size of 25 microns.
Preparation of carbon fiber/graphene/carbon microsphere composite powder
Adding 3kg of pre-oxidized carbon fiber short fibers and 2kg of carbon microsphere powder into 2kg of ferric nitrate nonahydrate and 50L of ethanol organic solvent, grinding zirconia balls with the diameter of 1mm for 0.5h, and controlling the ball milling temperature to be 20-30 ℃; ball-milling and drying to obtain a mixture of carbon fiber precursor powder with the particle size of 20-50 microns, carbon microspheres with the particle size of 20-25 microns and ferric nitrate nonahydrate; placing in an alumina crucible, transferring into a high temperature vapor deposition furnace, introducing nitrogen N for 5 min2For discharging air inside the tube; then the temperature is increased to 450 ℃ (the temperature increase rate is 20 ℃/min); keeping for half an hour, heating to 950 deg.C, and introducing methane and hydrogen H2(methane with Hydrogen H)2The mass ratio of (1): 4) preparing graphene through high-temperature deposition; wherein the nitrogen flow is always kept at 100sccm until the reaction is finished; methane and hydrogen H are turned off2Thereafter, the nitrogen N may be turned off2(ii) a And finally, collecting carbon fiber/graphene/carbon microsphere powder through a powder collector.
Preparation of composite graphene floor heating slurry
20 parts of carbon fiber/graphene/carbon microsphere powder, 60 parts of matrix binder (containing curing agent), 10 parts of dispersing aid BYK-190, 5 parts of leveling aid BYK-333, 4.5 parts of anti-settling agent fumed silica, 0.5 part of defoaming agent KS-66 and the like are sequentially added into a stirring cylinder and uniformly stirred, a three-roll mill is used for grinding until the discharge granularity is 5-10 mu m, the grinding temperature is 25-35 ℃, and then the composite graphene floor heating slurry can be obtained, wherein the square resistance of the composite graphene floor heating slurry is 300 omega/□, and the viscosity is 10000-13000 cps.
Other contents can refer to the first embodiment.
Example three:
the difference between the present embodiment and the first embodiment is: the mass ratio of the carbon fiber precursor powder to the carbon microspheres is different.
Specifically, the preparation method of the composite graphene floor heating slurry comprises the following steps:
preparation of preoxidized carbon fiber short fiber and carbon microsphere
(1) Pre-oxidized carbon fiber precursor (5kg) with the specification of 3K is placed into a disc extrusion type fiber cutting machine (3kW power), and the pre-oxidized carbon fiber precursor is cut into short fibers with the length of 3 mm.
(2) Preparing carbon microspheres by adopting a medium-temperature thermal polymerization method: taking medium-temperature coal pitch, putting the medium-temperature coal pitch into a pressurized and sealed reaction kettle, heating the pressure to be 1.0MPa and the temperature to be 350 ℃, stirring at the speed of 400r/min for 4 hours to obtain a carbon microsphere mixture, and extracting organic solvents of toluene and n-hexane to obtain carbon microspheres; drying and washing with ethanol to obtain the carbon microsphere with the particle size of 10 microns.
Preparation of carbon fiber/graphene/carbon microsphere composite powder
Adding 2kg of ferric nitrate nonahydrate and 50L of ethanol organic solvent into 5kg of pre-oxidized carbon fiber short fiber and 3kg of carbon microsphere powder, grinding zirconia balls with the diameter of 1mm for 0.5h, and controlling the ball milling temperature to be 20-30 ℃; ball-milling and drying to obtain a mixture of carbon fiber precursor powder with the particle size of 10-20 microns, carbon microspheres with the particle size of 5-10 microns and ferric nitrate nonahydrate; placing in an alumina crucible, transferring into a high temperature vapor deposition furnace, introducing nitrogen N for 5 min2For discharging air inside the tube; then the temperature is increased to 450 ℃ (the temperature increase rate is 20 ℃/min); keeping for half an hour, heating to 950 deg.C, and introducing methane and hydrogen H2(methane with Hydrogen H)2The mass ratio of (1): 4) preparing graphene through high-temperature deposition; wherein the nitrogen flow is always kept at 100sccm until the reaction is finished; methane and hydrogen H are turned off2Thereafter, the nitrogen N may be turned off2(ii) a And finally, collecting carbon fiber/graphene/carbon microsphere powder through a powder collector.
Preparation of composite graphene floor heating slurry
Sequentially adding 20 parts of carbon fiber/graphene/carbon microsphere powder, 60 parts of matrix binder (containing curing agent), 10 parts of dispersing aid BYK-190, 5 parts of leveling aid BYK-333, 4.5 parts of anti-settling agent fumed silica, 0.5 part of defoaming agent KS-66 and the like into a stirring cylinder, uniformly stirring, and grinding by using a three-roll machine until the discharge granularity is 5-10 mu m; the grinding temperature is 25-35 ℃, and the composite graphene floor heating slurry can be obtained, wherein the sheet resistance is 220 omega/□, and the viscosity is 10000-13000 cps.
Other contents can refer to the first embodiment.
Comparative example one:
preparation of carbon crystal conductive ink
And (2) sequentially adding 20 parts of carbon crystal powder, 60 parts of matrix binder (containing curing agent), 10 parts of dispersing aid BYK-190, 5 parts of leveling aid BYK-333, 3 parts of anti-settling agent fumed silica, 2 parts of water repellent agent XH-5160 and the like into a stirring cylinder, uniformly stirring, grinding by using a three-roll mill until the discharge granularity is 5-10 mu m, and the grinding temperature is 25-35 ℃, so as to obtain the carbon crystal conductive ink, wherein the sheet resistance is 430-510 omega/□, and the viscosity is 10000-13000 cps.
The floor heating pastes obtained in the first to third examples and the conductive ink obtained in the first comparative example are subjected to performance tests, and the results are analyzed as follows:
(1) according to the experimental results of the first embodiment and the second embodiment, the carbon fiber precursor powder and the carbon microspheres with different particle sizes have the influence on the effect of the composite graphene, and the carbon fiber precursor powder with the particle size of 10-20 μm has a good deposition effect; under the same proportion, the particle size of the precursor powder is small, and the conductive effect is good.
(2) The experimental results of the first embodiment and the third embodiment show that the initial content of the carbon fiber precursor powder and the carbon microspheres is increased in the preparation process of the carbon fiber/graphene/carbon microsphere powder, which is not beneficial to the effect of graphene compounding; under the same proportion, the smaller the initial content is, the better the conductive effect of the composite powder is.
(3) As can be seen from the comparison between the first example and the first comparative example, the temperature unevenness of the carbon crystal conductive ink coating is 6 to 7 ℃. The temperature unevenness of the composite graphene floor heating slurry is less than 5 ℃. Under the condition of being electrified at 297V for 300 hours, the carbon crystal printing ink is attenuated by about 7%, and the composite graphene floor heating slurry is attenuated by less than 5%.
In the above embodiments and alternatives, the specification of the pre-oxidized carbon fiber precursor may also be 1K, 2K, 4K, 5K, 6K, 7K, 8K, 9K, 10K, 11K, 12K; the carbon fiber staple fibers may also have a length of 1mm, 1.5mm, 2mm, 2.5mm, 3.5mm, 4mm, 5mm, 5.5mm, 6mm, or the like.
In the above embodiment and the alternative, the grinding conditions in the preparation process of the carbon fiber/graphene/carbon microsphere composite powder may also be: the zirconia balls as the ball milling media may have a diameter of 1.5mm, 2mm, 2.5mm, 3mm, etc., the ball milling time may be 0.1h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, the particle size of the carbon fiber precursor powder obtained by ball milling may be 18 μm, 16 μm, 15 μm, 12 μm, 10 μm, 8 μm, etc., and the particle size of the carbon microspheres obtained by ball milling may be 15 μm, 12 μm, 9 μm, 8 μm, 6 μm, 5 μm, etc.
In the above embodiments and their alternatives, the reaction conditions for the warm polymerization process in the pressurized and sealed reaction vessel may further be: the reaction temperature can be 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃ and the like, the stirring speed can be 100r/min, 200r/min, 300r/min, 600r/min, 700r/min and the like, and the reaction time can be 0.1h, 0.5h, 1h, 2h, 3h, 5h, 6h, 8h and the like.
In the above embodiments and alternatives thereof, the ethanol organic solvent may also be replaced by ethylene glycol or glycerol, and may also be replaced by a plurality of ethylene glycol, ethanol, and glycerol.
In the above embodiment and its alternative, the drying in the preparation process of the carbon fiber/graphene/carbon microsphere composite powder may be freeze drying, vacuum drying or heating and air-blast drying.
In the above embodiment and its alternative, the mass ratio of the carbon fiber precursor powder, the carbon microsphere powder, the ethanol organic solvent, and the ferric nitrate nonahydrate may also be 0.1: 1: 1: 0.1, 0.1: 0.5: 0.5: 1. 0.5: 0.5: 0.5: 0.8, 0.1: 0.6: 1: 0.3, 1: 0.5: 1: 0.5, 0.6: 0.8: 0.8: 0.2, 0.6: 0.4: 0.6: 0.3, etc.
In the above embodiments and the alternatives, the temperature rise of the high temperature vapor deposition furnace is divided into two stages, the target temperature of the first temperature rise stage may be 400 ℃, 500 ℃, 550 ℃, 600 ℃ or the like, and the target temperature of the second temperature rise stage may be 800 ℃, 900 ℃, 1000 ℃, 1200 ℃ or the like.
In the above embodiments and alternatives, the mass ratio of methane to hydrogen may also be 0.1: 1. 1: 1. 2: 1. 4: 1. 6: 1. 8: 1, etc.
In the above embodiment and the alternative scheme, the ball mill used for ball milling in the preparation process of the carbon fiber/graphene/carbon microsphere composite powder can be replaced by a sand mill or a blue mill.
In the above embodiment and its alternatives, the carbon fiber/graphene/carbon microsphere powder may also be in an amount of 0.1 parts, 1 part, 3 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, etc.; the weight portion of the matrix binder (containing the curing agent) can also be 0.1 portion, 5 portions, 10 portions, 20 portions, 30 portions, 40 portions, 50 portions, 70 portions and the like; the dispersing auxiliary BYK-190 can also be 0.1 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 3 parts, 4 parts and the like in parts by weight; the leveling assistant BYK-333 can also be 0.1 part, 0.5 part, 1 part, 1.5 parts, 2.5 parts, 3 parts, 4 parts and the like in parts by weight; the anti-settling agent fumed silica may be in an amount of 0.1 part, 0.5 part, 1 part, 1.5 parts, 2.5 parts, 3.5 parts, 4 parts, 5 parts, etc., and the defoaming agent KS-66 may be in an amount of 0.1 part, 0.3 part, 0.4 part, 0.6 part, 0.8 part, 0.9 part, etc. Of course, the types of the auxiliary agents are not limited to the above types, and other common types of auxiliary agents can be selected. Wherein, the matrix binder is polyurethane and/or epoxy resin with the molecular weight of 50000-100000, and preferably the epoxy resin.
In the above embodiment and the alternative scheme thereof, the three-roll mill in the preparation process of the composite graphene floor heating slurry can be replaced by a ball mill, a sand mill or a bluemill.
In the embodiment and the alternative scheme thereof, the sheet resistance of the composite graphene floor heating slurry can also be 40 Ω/□, 600 Ω/□, 1000 Ω/□, 1500 Ω/□, 2000 Ω/□, 3000 Ω/□, 3500 Ω/□, 4000 Ω/□ and the like; the viscosity of the composite graphene floor heating slurry can be 3000-5000 cps, 4000-6000 cps, 7000-1000 cps, 15000-20000 cps, 18000-22000 cps, 20000-23000 cps, 25000-28000 cps, 26000-30000 cps and the like.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. The authentication contents of the respective embodiments are not described one by one here.
The composite graphene floor heating slurry prepared from the carbon fiber/graphene/carbon microsphere composite powder has the characteristics of good adhesion, high conductivity, water resistance, alcohol resistance and the like; also has excellent conductive uniformity and anti-attenuation property.
The preparation method of the invention has simple process and easy operation, and also has the following advantages:
(1) the invention adopts a physical method to prepare micron-sized carbon fiber powder, and asphalt is used for preparing carbon microspheres; taking micron-sized carbon fiber powder and carbon microspheres as a graphene carrier substrate, and grinding and mixing ferric nitrate nonahydrate to the inner surface of the fiber to provide a growth point for the composite graphene; and (3) carrying out catalytic pyrolysis on methane and hydrogen to grow graphene, and carrying out high-temperature carbonization to prepare the carbon fiber/graphitized carbon microsphere/graphene composite powder.
(2) And filling carbon fiber/graphene/carbon microsphere composite powder serving as conductive filler into resin to obtain the composite graphene floor heating slurry with uniform resistance.
(3) The carbon microspheres are used as point-shaped particles and are uniformly dispersed in the organic filler, and the carbon fiber/graphene composite carbon microspheres are anchored in the resin, so that the composite graphene floor heating slurry is favorably stored for a long time and is not deteriorated; the printed electric heating coating has even resistance and the film layer generates heat evenly.
(4) The heating product prepared from the composite graphene floor heating slurry improves the resistance uniformity, prolongs the service life and the like.
The above "/" means sum.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (6)
1. The composite graphene floor heating slurry is characterized by comprising the following components in parts by weight: 0.1-30 parts of carbon fiber/graphene/carbon microsphere powder, 0.1-70 parts of matrix binder, 0.1-5 parts of dispersing agent, 0.1-5 parts of flatting agent, 0.1-5 parts of anti-settling agent and 0.1-1 part of defoaming agent;
the carbon fiber/graphene/carbon microsphere powder is prepared by growing graphene on the surfaces of carbon fibers and carbon microspheres through vapor deposition;
the matrix binder is polyurethane and/or epoxy resin with the molecular weight of 50000-100000, and the anti-settling agent is fumed silica; the sheet resistance of the composite graphene floor heating slurry is 40-4000 omega/□, the viscosity is 3000-30000 cps, and the granularity is 5-10 mu m;
the preparation method of the composite graphene floor heating slurry comprises the following steps:
(1) preparing carbon fiber/graphene/carbon microsphere powder;
(2) mixing carbon fiber/graphene/carbon microsphere powder, matrix binder, dispersant, flatting agent, anti-settling agent and defoamer according to a preset proportion, grinding and stirring to obtain composite graphene floor heating slurry;
wherein the step (1) comprises the following steps:
(11) cutting the pre-oxidized carbon fiber precursor into short fibers with target length; taking coal pitch as a raw material, generating a carbon microsphere mixture in a reaction kettle by adopting a medium-temperature thermal polymerization method, and separating and extracting by using an organic solvent to obtain carbon microsphere powder;
(12) mechanically dispersing short fibers and carbon microsphere powder in an organic solvent II, adding ferric nitrate nonahydrate, mechanically mixing, drying to obtain powder, transferring to an alumina crucible for high-temperature carbonization, carrying out vapor deposition on graphene in a high-temperature vapor deposition furnace to obtain carbon fiber/graphene/carbon microsphere powder, and finally collecting the carbon fiber/graphene/carbon microsphere powder through a powder collector.
2. The composite graphene floor heating slurry according to claim 1, wherein the specification of the pre-oxidized carbon fiber precursor is 1-12K; the length of the short fiber is 1-6 mm; the coal pitch is medium-temperature coal pitch; the organic solvent I is toluene and n-hexane; the reaction conditions of the medium-temperature thermal polymerization method are as follows: the temperature is 300-400 ℃, the stirring speed is 100-700 r/min, the pressure is 1.0MPa, and the time is 0.1-8 h.
3. The composite graphene floor heating slurry according to claim 1, wherein the specification of the pre-oxidized carbon fiber precursor is 1-3K; the length of the short fiber is 1-3 mm.
4. The composite graphene floor heating slurry according to claim 1, wherein the mechanical dispersing manner in the step (12) is a ball mill, a sand mill or a Langmuir mill; when the mechanical dispersion mode is a ball mill, the ball milling medium is zirconia balls with the diameter of 1-3 mm, the ball milling time is 0.1-4 h, the ball milling temperature is controlled to be 20-30 ℃, the particle size of carbon fiber precursor powder obtained by ball milling is not more than 20 microns, and the particle size of carbon microsphere powder is 5-15 microns; the organic solvent II is one or more of glycol, ethanol and glycerol; the drying mode is freeze drying, vacuum drying or heating blast drying; the mass ratio of the carbon fiber precursor powder to the carbon microsphere powder to the organic solvent II to the ferric nitrate nonahydrate is (0.1-1): 0.1-1: 0.1-1: 0.1 to 1.
5. The composite graphene floor heating slurry according to claim 1, wherein the vapor deposition conditions are as follows: in a high-temperature vapor deposition furnace, methane and hydrogen are used as gas sources, nitrogen is used as a protective gas source, and the temperature is 800-1200 ℃.
6. The composite graphene floor heating slurry according to claim 5, wherein the mass ratio of methane to hydrogen is 0.1-8: 1.
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| CN107910445A (en) * | 2017-11-06 | 2018-04-13 | 西安交通大学 | A kind of perovskite solar cell of two-layer electrode and preparation method thereof |
| CN109280425A (en) * | 2018-11-02 | 2019-01-29 | 杭州超探新材料科技有限公司 | A kind of preparation method of floor heating electric hot plate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085873A (en) * | 2014-06-03 | 2014-10-08 | 张映波 | Method for preparing carbon nanotube on fiber surface in high density |
| CN104693897A (en) * | 2015-02-28 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Conductive ink based on graphene composite material and preparation method thereof |
| CN107910445A (en) * | 2017-11-06 | 2018-04-13 | 西安交通大学 | A kind of perovskite solar cell of two-layer electrode and preparation method thereof |
| CN109280425A (en) * | 2018-11-02 | 2019-01-29 | 杭州超探新材料科技有限公司 | A kind of preparation method of floor heating electric hot plate |
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