CN114163825A - Core-shell structure graphene composite particle and preparation method thereof - Google Patents
Core-shell structure graphene composite particle and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 136
- 239000011246 composite particle Substances 0.000 title claims abstract description 79
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 113
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 30
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 230000010355 oscillation Effects 0.000 description 6
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- VVSMKOFFCAJOSC-UHFFFAOYSA-L disodium;dodecylbenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1 VVSMKOFFCAJOSC-UHFFFAOYSA-L 0.000 description 3
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C08J3/00—Processes of treating or compounding macromolecular substances
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Abstract
The invention provides a core-shell structure graphene composite particle and a preparation method thereof, wherein the preparation method comprises the following steps: step one, placing graphene in an organic solvent for mixing; step two, putting the emulsifier into deionized water for heating and stirring; mixing ethyl cellulose, epoxy resin and an organic solvent; adding the mixed graphene solution into the oil phase solution, and stirring simultaneously; step five, stirring the oil phase solution by a stirrer, and volatilizing the organic solvent during stirring; adding the oil phase solution into the water phase solution, stirring, heating and continuing stirring after the organic solvent is completely volatilized until the ethyl cellulose is solidified; and seventhly, carrying out vacuum filtration on the composite particles through filter cloth, washing with deionized water, and then putting into a freeze drying oven for drying treatment. The composite particles prepared by the method have consistent particle size, the graphene is not easy to fall off, the sphericity is good, and the fluidity and the like meet the jet printing conditions.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a core-shell structure graphene composite particle and a preparation method thereof.
Background
Graphene has found much attention as a two-dimensional network of closely packed six-membered rings formed by hybridization of carbon atoms in sp 2. The graphene has excellent properties of good performance control surface, excellent mechanical property, ultra-high specific surface area and the like, and meanwhile, the unique two-dimensional structure of the graphene has the characteristics of good conductivity, special boundary effect and the like through research. The theoretical Young modulus is as high as 1.0TPa, and the inherent tensile strength is as high as 130 GPa. Meanwhile, the graphene is also a zero-distance semiconductor, and has better physical and chemical properties compared with the traditional semiconductor. Graphene has excellent optical properties, the absorption rate in a wide wavelength range is only 2.3%, the graphene is almost transparent when seen by naked eyes, the absorption rate is increased by 2.3% when each layer is stacked, the specific surface area of the graphene is up to 2630m2/g, the specific surface area of only 3 g of graphene is enough to be comparable to the floor area of a football field, due to the ultrahigh specific surface area of the graphene, the graphene is easy to agglomerate, and the graphene is difficult to be uniformly dispersed by the conventional process.
In recent years, the injection molding technology has become one of the research hotspots and development trends in the material science and engineering industries. The particles are accelerated by high-pressure gas, and the particles are directly sprayed and printed on a matrix material to be prepared, so that the ordered dispersion of the coated particles is realized. The method can effectively meet the requirement on dispersion precision and can locally control dispersion or concentration. According to the invention, graphene which is difficult to disperse is made into composite particles, so that the dispersion of the graphene in the composite particles is realized, and a base material is provided for jet printing.
In view of the fact that the traditional preparation method cannot prepare the composite particles meeting the requirement of jet printing forming, a novel process is adopted to prepare the graphene composite particles.
Disclosure of Invention
The invention aims to solve the technical problem of providing core-shell structure graphene composite particles and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of core-shell structure graphene composite particles comprises the following steps:
step one, placing graphene in an organic solvent for mixing;
step two, putting the emulsifier into deionized water for heating and stirring, and putting aside for standby after stirring;
step three, stirring and mixing ethyl cellulose, epoxy resin and an organic solvent;
step four, adding the graphene solution mixed in the step one into the oil phase solution in the step three, and stirring simultaneously;
step five, stirring the oil phase solution added with the graphene by a stirrer, and volatilizing the organic solvent during stirring;
step six, adding the oil phase solution into the water phase solution obtained in the step two, stirring, heating and continuing stirring after the organic solvent is completely volatilized until the ethyl cellulose is solidified;
and seventhly, carrying out vacuum filtration on the composite particles through filter cloth, washing the composite particles for multiple times through deionized water, and then putting the composite particles into a freeze drying oven for drying treatment to obtain the core-shell structure graphene composite particles.
In a preferred embodiment, in the first step and the third step, the organic solvent is dichloromethane, alcohol, diethyl ether, toluene or chloroform.
In a preferred scheme, in the first step, dichloromethane is used as an organic solvent, 0.3-0.6 part of graphene is placed in 110-125 parts of dichloromethane solution, the graphene needs to be added firstly, and then the dichloromethane solution is slowly added into a container for containing the graphene.
In a preferred embodiment, in the first step, graphene is placed in an organic solvent, and then placed in an ultrasonic device for dispersion.
In the preferred scheme, the ultrasonic vibration time of the ultrasonic device is set to be 15min, the ultrasonic frequency is 50KHz, and the heating temperature is 40 ℃.
In a preferred scheme, in the second step, 4-6.5 parts of emulsifier is weighed and placed in 140-155 parts of deionized water for heating and stirring, wherein the heating temperature is 50 ℃, the heating and stirring time is 30min, and the stirring speed is 600 r/min.
In a preferable scheme, in the third step, 1.8-2.5 parts of ethyl cellulose and 2.4-2.6 parts of epoxy resin are weighed and placed in 125 parts of organic solution for stirring, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the preparation method is implemented after the ethyl cellulose and the epoxy resin are melted.
In a preferred scheme, in the fifth step, the oil phase solution added with the graphene is stirred by a stirrer, the stirring speed is adjusted to 700 r/min-850 r/min, the heating temperature is 30 ℃, and the organic solvent is volatilized during stirring.
In a preferable scheme, in the sixth step, the stirring speed is adjusted to 950 r/min-1150 r/min, the heating temperature is 40 ℃, and the stirring is carried out for 3 hours.
The invention also provides the graphene composite particles with the core-shell structure, which comprise an epoxy resin core material, wherein the outer side of the epoxy resin core material is coated with a graphene cellulose hybrid layer.
According to the core-shell structure graphene composite particle and the preparation method thereof, the composite particle prepared through the emulsification reaction has good sphericity, the graphene is uniformly mixed in the composite particle in an ultrasonic wave and stirring mode, and the shell can effectively prevent the graphene from falling off. The prepared composite particle composite jet printing process has the required sphericity and particle size. The micron-sized spherical composite particles can effectively reduce the condition of blocking the spray pipe, and the process for manufacturing the composite particles is simple and efficient, the powder collection rate is high, and the composite particles are not adhered to each other.
Drawings
The invention is further illustrated with reference to the accompanying drawings and examples:
fig. 1 shows the composite particles without added graphene;
FIG. 2 is a schematic structural view of a composite fine particle of the present invention;
FIG. 3 is a scanning electron microscope image of the morphology of the composite particles without added graphene;
FIG. 4 is a scanning electron microscope picture of the morphology of the core-shell graphene composite particles;
in the figure: the composite material comprises an epoxy resin core material 1, an ethyl cellulose wall material 2 and a graphene cellulose mixed layer 3.
Detailed Description
A core-shell structure graphene composite particle for jet printing molding adopts a microemulsion method, adopts an oil-in-water emulsion reaction, takes ethyl cellulose as a wall material and epoxy resin as a core material, and comprises the following components in parts by mass: 1.8-2.5 parts of epoxy resin: 2.4-2.6 parts of graphene is mixed with an organic solvent to be used as an oil phase, 0.3-0.6 part of graphene is placed in the organic solvent and placed in an ultrasonic device for preliminary dispersion, and then the graphene solution is mixed with the oil phase. And finally, slowly pouring the oil phase into the water phase, and uniformly dispersing the graphene which is difficult to disperse into the prepared composite microspheres in a mechanical stirring manner.
The composite particle core material is one of epoxy resin E-44, epoxy resin E-51 and epoxy resin E-44, and the epoxy resin E-44 is easily dissolved in an oil phase solvent.
The composite particle wall material is ethyl cellulose produced by Chinese medicines, and the quality of the solidified wall material is ensured by high-purity ethyl cellulose.
The organic solvent is one of dichloromethane, alcohol, ether, toluene and chloroform, wherein a dichloromethane solution is preferred, the boiling point is low, the solvent can volatilize at a lower temperature, and the solvent has better solubility on the wall material of the core material.
The emulsifier is one or more of sodium dodecyl benzene sulfonate, gelatin, Arabic gum, sodium dodecyl benzene sulfate and the like, and the gelatin and the sodium dodecyl benzene sulfonate are preferably used as the emulsifier.
The graphene is self-made reduced graphene oxide, is obtained by reducing graphene oxide, has unreduced groups on the surface, improves the solubility of the graphene in a solution, and is easy to disperse.
A preparation method of core-shell structure graphene composite particles for jet printing forming comprises the following steps:
step one, weighing 0.3-0.6 part of graphene, placing the graphene into 110-125 parts of dichloromethane solution, adding the graphene, slowly adding the dichloromethane solution into a beaker along a glass rod to prevent the graphene from drifting, placing the beaker into an ultrasonic device for ultrasonic operation, setting the ultrasonic vibration time for 15min, the ultrasonic frequency for 50KHz, and the heating temperature for 40 ℃.
And step two, weighing 4-6.5 parts of emulsifier, placing the emulsifier in 140-155 parts of deionized water, heating and stirring at 50 ℃ for 30min at a stirring speed of 600r/min, and placing aside for later use after stirring.
Step three, weighing 1.8-2.5 parts of ethyl cellulose and 2.4-2.6 parts of epoxy resin, placing the mixture into 125 parts of dichloromethane solution, stirring at the stirring speed of 450r/min and the heating temperature of 30 ℃, and placing the mixture for later use after the mixture is melted. The composite particles prepared by mixing ethyl cellulose and epoxy resin, as shown in fig. 1, include an epoxy resin core material and an ethyl cellulose wall material, and fig. 3 is a scanning electron microscope picture of the composite particles without graphene material.
And step four, slowly adding the graphene into the oil phase solution obtained in the step three after the ultrasonic oscillation is finished, slowly remaining the graphene along a glass rod in the adding process, and stirring the solution at the rotation speed of 200r/min to prevent the graphene from agglomerating.
And step five, stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 700 r/min-850 r/min, heating to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the oil phase solution is reduced to below 125 ml.
And step six, slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 950 r/min-1150 r/min, heating the solution to 40 ℃, stirring the solution for 3 hours, raising the temperature to 45 ℃ after the dichloromethane solution is completely volatilized, and continuing stirring the solution until the ethyl cellulose is solidified.
And seventhly, carrying out vacuum filtration on the composite particles through filter cloth, washing the composite particles for multiple times through deionized water, and then putting the composite particles into a freeze drying oven for drying treatment to obtain the core-shell structure graphene composite particles.
The core-shell structure graphene composite particle prepared by the preparation method comprises an epoxy resin core material, and a graphene cellulose hybrid layer is coated on the outer side of the epoxy resin core material, as shown in fig. 2.
Example 1:
in the embodiment, 0.4 part of graphene is weighed and placed in 115 parts of dichloromethane solution, and then placed in an ultrasonic device for ultrasonic operation, wherein the ultrasonic vibration time is set to be 15min, the ultrasonic frequency is set to be 50KHz, and the heating temperature is set to be 40 ℃. Weighing 4.5 parts of gelatin, placing the gelatin in 150 parts of deionized water, heating and stirring at the temperature of 50 ℃ for 30min at the stirring speed of 600r/min, and placing aside for later use after stirring to serve as a water phase; 2.5 parts of ethyl cellulose and 2.5 parts of E-51 resin are weighed and placed in 125 parts of dichloromethane solution for stirring, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the mixture can be placed aside for standby after being melted. After the graphene is subjected to ultrasonic oscillation, the graphene is slowly added into the oil phase solution, the graphene needs to be slowly left along a glass rod in the adding process, and the solution is stirred at the rotating speed of 200r/min, so that the graphene is prevented from agglomerating. Stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 800r/min, heating the solution to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the volume of the oil phase solution is reduced to below 125 ml. Slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 1000r/min, heating the solution to 40 ℃, stirring the solution for 3h, heating the solution to 45 ℃ after the dichloromethane solution is completely volatilized, and continuously stirring the solution until the ethyl cellulose is solidified. And cooling the solution to room temperature, filtering by using a vacuum suction filtration suction filter, washing for 2-3 times by using deionized water, and drying the obtained composite particles in a freeze dryer. And obtaining the required graphene composite particles.
Detecting relevant parameters of the prepared core-shell structure graphene composite particles: apparent density: 0.66g/cm3Tap density: 0.71g/cm3Fluidity: 1.44s/5g, and the size of the composite particles is 80-650 um.
Example 2:
weighing 0.4 part of graphene, placing the graphene in 115 parts of dichloromethane solution, then placing the graphene in an ultrasonic device for ultrasonic operation, and setting ultrasonic vibration time for 15min, ultrasonic frequency for 50KHz and heating temperature for 40 ℃. Weighing 4 parts of gelatin and 0.5 part of sodium dodecyl benzene sulfonate, placing the gelatin and the sodium dodecyl benzene sulfonate in 150 parts of deionized water, heating and stirring at the temperature of 50 ℃ for 30min at the stirring speed of 600r/min, and placing aside for later use after stirring to serve as a water phase; 2.3 parts of ethyl cellulose and 2.4 parts of E-51 resin are weighed and placed in 125 parts of dichloromethane solution for stirring, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the mixture can be placed aside for standby after being melted. After the graphene is subjected to ultrasonic oscillation, the graphene is slowly added into the oil phase solution, the graphene needs to be slowly left along a glass rod in the adding process, and the solution is stirred at the rotating speed of 200r/min, so that the graphene is prevented from agglomerating. Stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 850r/min, heating the solution to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the volume of the oil phase solution is reduced to below 125 ml. Slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 950r/min, heating the solution to 40 ℃, stirring the solution for 3 hours, and after the dichloromethane solution is completely volatilized, heating the solution to 45 ℃ and continuously stirring the solution until the ethyl cellulose is solidified. And cooling the solution to room temperature, filtering by using a vacuum suction filtration suction filter, washing for 2-3 times by using deionized water, and drying the obtained composite particles in a freeze dryer. And obtaining the required graphene composite particles.
Detecting relevant parameters of the prepared graphene composite particles with the core-shell structure: apparent density: 0.70g/cm3Tap density: 0.78g/cm3Fluidity: 1.34s/5g, and the size of the composite particles is 70-550 um.
Example 3:
weighing 0.4 part of graphene, placing the graphene in 115 parts of dichloromethane solution, then placing the graphene in an ultrasonic device for ultrasonic operation, and setting ultrasonic vibration time for 15min, ultrasonic frequency for 50KHz and heating temperature for 40 ℃. Weighing 4.5 parts of gelatin and 0.4 part of sodium dodecyl benzene sulfate, placing the gelatin and the sodium dodecyl benzene sulfate into 150 parts of deionized water, heating and stirring at the temperature of 50 ℃ for 30min at the stirring speed of 600r/min, and placing the mixture aside for later use as a water phase after stirring; 2.1 parts of ethyl cellulose and 2.4 parts of E-44 resin are weighed and placed in 125 parts of dichloromethane solution for stirring, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the mixture can be placed aside for standby after being melted. After the graphene is subjected to ultrasonic oscillation, the graphene is slowly added into the oil phase solution, the graphene needs to be slowly left along a glass rod in the adding process, and the solution is stirred at the rotating speed of 200r/min, so that the graphene is prevented from agglomerating. Stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 800r/min, heating the solution to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the volume of the oil phase solution is reduced to below 125 ml. Slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 1000r/min, heating the solution to 40 ℃, stirring the solution for 3h, heating the solution to 45 ℃ after the dichloromethane solution is completely volatilized, and continuously stirring the solution until the ethyl cellulose is solidified. And cooling the solution to room temperature, filtering by using a vacuum suction filtration suction filter, washing for 2-3 times by using deionized water, and drying the obtained composite particles in a freeze dryer. And obtaining the required graphene composite particles.
Detecting relevant parameters of the prepared core-shell structure graphene composite particles: apparent density: 0.72g/cm3Tap density: 0.77g/cm3Fluidity: 1.30s/5g, and the size of the composite particles is 85-500 um.
Example 4:
weighing 0.4 part of graphene, placing the graphene in 115 parts of dichloromethane solution, then placing the graphene in an ultrasonic device for ultrasonic operation, and setting ultrasonic vibration time for 15min, ultrasonic frequency for 50KHz and heating temperature for 40 ℃. Weighing 2.5 parts of gelatin and 2 parts of Arabic gum, placing in 150 parts of deionized water, heating and stirring at 50 ℃ for 30min at a stirring speed of 600r/min, and placing aside for later use as a water phase after stirring; weighing 1.8 parts of ethyl cellulose and 2.6 parts of E-44 resin, placing the mixture into 125 parts of dichloromethane solution, stirring at the stirring speed of 450r/min and the heating temperature of 30 ℃, and placing the mixture for later use after the mixture is melted. After the graphene is subjected to ultrasonic oscillation, the graphene is slowly added into the oil phase solution, the graphene needs to be slowly left along a glass rod in the adding process, and the solution is stirred at the rotating speed of 200r/min, so that the graphene is prevented from agglomerating. Stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 800r/min, heating the solution to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the volume of the oil phase solution is reduced to below 125 ml. Slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 1000r/min, heating the solution to 40 ℃, stirring the solution for 3h, heating the solution to 45 ℃ after the dichloromethane solution is completely volatilized, and continuously stirring the solution until the ethyl cellulose is solidified. And cooling the solution to room temperature, filtering by using a vacuum suction filtration suction filter, washing for 2-3 times by using deionized water, and drying the obtained composite particles in a freeze dryer. And obtaining the required graphene composite particles.
Detecting relevant parameters of the prepared core-shell structure graphene composite particles: apparent density: 0.77g/cm3Tap density: 0.82g/cm3Fluidity: 1.45s/5g, and the size of the composite particles is 60-450 um.
Example 5:
weighing 0.4 part of graphene, placing the graphene in 115 parts of dichloromethane solution, then placing the graphene in an ultrasonic device for ultrasonic operation, and setting ultrasonic vibration time for 15min, ultrasonic frequency for 50KHz and heating temperature for 40 ℃. Weighing 4.5 parts of gelatin and 0.5 part of sodium dodecyl benzene sulfonate, placing the gelatin and the sodium dodecyl benzene sulfonate in 150 parts of deionized water, heating and stirring at the temperature of 50 ℃ for 30min at the stirring speed of 600r/min, and placing the mixture aside for later use as a water phase after stirring; 2.4 parts of ethyl cellulose and 2.5 parts of E-44 resin are weighed and placed in 125 parts of dichloromethane solution for stirring, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the mixture can be placed aside for standby after being melted. After the graphene is subjected to ultrasonic oscillation, the graphene is slowly added into the oil phase solution, the graphene needs to be slowly left along a glass rod in the adding process, and the solution is stirred at the rotating speed of 200r/min, so that the graphene is prevented from agglomerating. Stirring the oil phase solution added with the graphene by a stirrer, adjusting the stirring speed to 750r/min, heating the solution to 30 ℃, volatilizing dichloromethane during stirring, and stopping stirring when the volume of the oil phase solution is reduced to below 125 ml. Slowly adding the oil phase solution into the water phase solution along a glass rod, adjusting the stirring speed to 1050r/min, heating the solution to 40 ℃, stirring the solution for 3 hours, and after the dichloromethane solution is completely volatilized, heating the solution to 45 ℃ and continuously stirring the solution until the ethyl cellulose is solidified. And cooling the solution to room temperature, filtering by using a vacuum suction filtration suction filter, washing for 2-3 times by using deionized water, and drying the obtained composite particles in a freeze dryer. And obtaining the required graphene composite particles.
Detecting relevant parameters of the prepared core-shell structure graphene composite particles: apparent density: 0.81g/cm3Tap density: 0.86g/cm3Fluidity: 1.54s/5g, and the size of the composite particles is 50-350 um, which is shown in figure 4.
In the invention, the composite particles mainly comprise a core-shell structure of particles formed by ethyl cellulose and epoxy resin, the ethyl cellulose and graphene are bonded by using the epoxy resin as a core material, the ethyl cellulose is used as a wall material, and the shell of the composite particles is formed by heating and curing. The method has simple process, environment-friendly, nontoxic and harmless materials, and is suitable for jet printing and forming.
Scanning the prepared graphene composite particles by an SEM (scanning electron microscope), and observing the distribution of the graphene and the particle size of the composite particles as shown in figure 4. Loose density test platform is measured for self-control fixed quantity container, places the funnel top with the compound particle of graphite alkene and passes through the mode of vibration under the same frequency, falls to and surveys loose density in the long-pending container of constant volume, guarantees the particle free fall, and no obvious collision takes place between the granule. Tap density is measured after the vibrating table is vibrated. The mobility is through putting graphite alkene composite particle in the vibrating motor funnel, measures the mobility through the funnel mould of diameter 5mm, because the sphericity is good, does not take place blocking phenomenon, and composite particle surface graphite alkene does not take place to drop moreover.
Claims (10)
1. A preparation method of core-shell structure graphene composite particles is characterized by comprising the following steps:
step one, placing graphene in an organic solvent for mixing;
step two, putting the emulsifier into deionized water for heating and stirring, and putting aside for standby after stirring;
step three, stirring and mixing ethyl cellulose, epoxy resin and an organic solvent;
step four, adding the graphene solution mixed in the step one into the oil phase solution in the step three, and stirring simultaneously;
step five, stirring the oil phase solution added with the graphene by a stirrer, and volatilizing the organic solvent during stirring;
step six, adding the oil phase solution into the water phase solution obtained in the step two, stirring, heating and continuing stirring after the organic solvent is completely volatilized until the ethyl cellulose is solidified;
and seventhly, carrying out vacuum filtration on the composite particles through filter cloth, washing the composite particles for multiple times through deionized water, and then putting the composite particles into a freeze drying oven for drying treatment to obtain the core-shell structure graphene composite particles.
2. The method for preparing the core-shell graphene composite particle according to claim 1, wherein in the first step and the third step, the organic solvent is dichloromethane, alcohol, diethyl ether, toluene or chloroform.
3. The preparation method of the core-shell graphene composite particle according to claim 2, wherein in the first step, the organic solvent is dichloromethane, 0.3-0.6 part of graphene is placed in 110-125 parts of dichloromethane solution, the graphene needs to be added first, and then the dichloromethane solution is slowly added into a container for holding the graphene.
4. The method for preparing core-shell graphene composite particles according to claim 1, wherein in the first step, graphene is placed in an organic solvent and then placed in an ultrasonic device for dispersion.
5. The preparation method of the core-shell graphene composite particle according to claim 4, wherein the ultrasonic operation of the ultrasonic device sets an ultrasonic vibration time of 15min, an ultrasonic frequency of 50KHz, and a heating temperature of 40 ℃.
6. The preparation method of the core-shell graphene composite particle according to claim 1, wherein in the second step, 4-6.5 parts of emulsifier is weighed and placed in 140-155 parts of deionized water for heating and stirring, wherein the heating temperature is 50 ℃, the heating and stirring time is 30min, and the stirring speed is 600 r/min.
7. The preparation method of the core-shell graphene composite particle according to claim 1, wherein in the third step, 1.8-2.5 parts of ethyl cellulose and 2.4-2.6 parts of epoxy resin are weighed and placed in 125 parts of organic solution to be stirred, the stirring speed is 450r/min, the heating temperature is 30 ℃, and the core-shell graphene composite particle is prepared after the two are melted.
8. The preparation method of the core-shell graphene composite particles according to claim 1, wherein in the fifth step, the oil phase solution added with the graphene is stirred by a stirrer, the stirring speed is adjusted to 700 r/min-850 r/min, the heating temperature is 30 ℃, and the organic solvent is volatilized during stirring.
9. The preparation method of the core-shell graphene composite particles according to claim 1, wherein in the sixth step, the stirring speed is adjusted to 950 r/min-1150 r/min, the heating temperature is 40 ℃, and the stirring is carried out for 3 hours.
10. The graphene composite particles with the core-shell structure are characterized by comprising an epoxy resin core material, wherein the outer side of the epoxy resin core material is coated with a graphene cellulose hybrid layer.
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