CN111470491B - Carbonaceous hybrid powder and preparation method thereof - Google Patents
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Abstract
The invention provides a carbonaceous hybrid powder and a preparation method thereof, wherein the method comprises the following steps: dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion; mixing two-dimensional graphene oxide with a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion liquid, and performing solvent removal granulation on the second aqueous dispersion liquid to obtain hybridized carbon spheres; dispersing the hybridized carbon spheres in the first aqueous dispersion liquid to obtain a third aqueous dispersion liquid; and the third aqueous dispersion is subjected to drying, reduction and crushing treatment to obtain the carbonaceous hybrid powder. The method disclosed by the invention is simple in process, environment-friendly, pollution-free and suitable for industrial mass production, and the obtained carbonaceous hybrid powder is stable in structure, excellent in performance and good in application prospect.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to carbonaceous hybrid powder and a preparation method thereof.
Background
Carbon is one of the most common elements in nature, and has been widely used in low-end fields such as electrodes, brushes, coke iron-making, etc. for a long time because of its excellent thermal conductivity, electrical conductivity, etc. Since 2014 Andre Geim and Konstantin Novoselov have peeled graphene from transparent adhesive tapes, various carbon materials have been expected. Such carbon materials include zero-dimensional carbon black, acetylene black, ketjen black, conductive carbon black (SP), onion carbon, fullerenes, carbon quantum dots, one-dimensional carbon nanotubes, carbon fibers, two-dimensional graphene, graphite alkyne, multi-layer graphite nanofilm, and three-dimensional graphite, carbon aerogel, graphene foam, and the like.
These carbon materials have a certain self-limit when used alone. If graphene is used alone as a lithium conductive agent, the large lamellar structure of the graphene can cause a certain obstruction to lithium ion transmission, so that a graphene/carbon nanotube hybrid structure or a graphene/carbon black hybrid structure is commonly adopted to construct an effective conductive network at present. The use of carbon black/carbon fiber hybrid materials in rubber systems is more advantageous to improve the mechanical properties of the rubber than the use of carbon black alone in rubber systems. By carrying out composite construction on carbon materials with different dimensions, the structures and the properties of the carbon materials can be complemented, so that the synergistic effect of the carbon materials is exerted to the greatest extent, and the carbon materials show more excellent performances than any single carbon material, including isotropy, better dispersion performance, higher specific surface area, higher conductivity, higher mechanical performance and the like.
At present, research reports on composite construction of zero-dimensional carbon materials and one-dimensional carbon materials are presented. For example, chinese patent CN 104282914a discloses an ultrasonic dispersion method in which acetylene black and ball-milled carbon fibers are added into an ethanol solution, so as to obtain a powder conductive agent for lithium-sulfur battery by compounding, and the conductive agent is used in a sulfur positive electrode to facilitate formation of a good conductive network, improve conductivity of the positive electrode material, and further improve discharge capacity of the battery. However, the composite carbon material obtained by the method is unstable in structure, and acetylene black and carbon fibers do not form good combination. Chinese patent CN 108047495a discloses a super strong composite material for in-situ synthesis of carbon nanotubes and carbon black, which uses carbon nanotubes as main line, so that the generated carbon black particles are in a perfect grape-like structure in the form of beads. However, the temperature required by the in-situ preparation method is as high as 1400-1700 ℃, the required cost is high, and the industrialization application of the method is limited. Chinese patent CN109825131A discloses a composite carbon conductive ink, which is prepared by firstly synthesizing one-dimensional carbon fiber/gas phase carbon tube composite powder in a high temperature carbonization furnace at 800-1200 ℃, and blending zero-dimensional carbon black with the one-dimensional carbon fiber/gas phase carbon tube composite powder through a resin binder, a dispersing agent, a leveling agent, an anti-settling agent and a water repellent agent on the basis. However, this method requires various solvents such as binders and the like, and may further affect the carbon content of the material.
It is noted that the information disclosed in the foregoing background section is only for enhancement of understanding of the background of the invention and therefore it may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides a preparation method of a carbonaceous hybrid powder and the obtained carbonaceous hybrid powder, so as to solve the problems of complex process, high cost, unfriendly environment, low quality of the obtained product and the like of the existing method for constructing the composite of a zero-dimensional carbon material and a one-dimensional carbon material.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of carbonaceous hybrid powder, which comprises the following steps: dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion; mixing two-dimensional graphene oxide with a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion liquid, and performing solvent removal granulation on the second aqueous dispersion liquid to obtain hybridized carbon spheres; dispersing the hybridized carbon spheres in the first aqueous dispersion liquid to obtain a third aqueous dispersion liquid; and the third aqueous dispersion is dried, reduced and crushed to obtain the carbonaceous hybrid powder.
According to one embodiment of the present invention, the one-dimensional carbon nanotubes are selected from one or more of carbon nanotubes, hydroxylated carbon nanotubes and carboxylated carbon nanotubes, the carbon nanotubes comprising single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
According to one embodiment of the invention, the concentration of the first aqueous dispersion is between 0.1mg/mL and 5mg/mL; the concentration of the second aqueous dispersion liquid is 0.1 mg/mL-30 mg/mL, and the mass ratio of the two-dimensional graphene oxide to the zero-dimensional carbon material in the second aqueous dispersion liquid is (1-10) (0.1-5); the concentration of the third aqueous dispersion liquid is 0.1 mg/mL-50 mg/mL, and the mass ratio of the hybridized carbon spheres to the one-dimensional carbon nano tubes in the third aqueous dispersion liquid is (1-10) (0.1-2).
According to one embodiment of the present invention, the length of the one-dimensional carbon nanotube is 1 μm to 20 μm, and the diameter of the hybrid carbon sphere is 500nm to 5 μm.
According to one embodiment of the invention, the zero-dimensional carbon material is selected from one or more of acetylene black, conductive carbon black, ketjen black, carbon black, fullerenes, carbon quantum dots, and onion carbon.
According to one embodiment of the invention, the desolventizing granulation is performed by adopting a spray granulation mode, the working temperature of the spray granulation is 110-150 ℃, the working pressure is 0.1-0.3 MPa, and the working flow rate is 300-1800 mL/h.
According to one embodiment of the invention, the hybrid carbon spheres are dispersed in the first aqueous dispersion in a manner of low-speed magnetic stirring, the rotation speed of the low-speed magnetic stirring is 50-100 rpm/min, and the treatment time is 1-10 min.
According to one embodiment of the invention, the first aqueous dispersion and the second aqueous dispersion are each independently selected from one or more of ultrasonic dispersion, mechanical stirrer, high-speed shear disperser and homogenizer.
According to one embodiment of the invention, the third dispersion is subjected to freeze-drying, thermal reduction and mechanical pulverization in sequence to obtain the carbonaceous hybrid powder.
The invention also provides a carbonaceous hybrid powder, which is obtained by adopting the preparation method.
According to the technical scheme, the beneficial effects of the invention are as follows:
according to the preparation method of the carbon hybrid powder, the two-dimensional graphene oxide and the zero-dimensional carbon material are hybridized to construct the hybrid carbon material with the oxygen-containing functional groups on the surface, the hybrid carbon material is dispersed in the aqueous dispersion liquid containing the carbon nano tubes, the stably dispersed zero-dimensional carbon spheres and the one-dimensional carbon nano tube hybridized aqueous composite dispersion liquid can be formed through electrostatic repulsion, and the carbon hybrid powder is obtained after drying and reduction treatment. The method is carried out in an aqueous system, does not need solvents such as a surfactant, a binder and the like, has no toxicity and no pollution in the process flow, and is suitable for industrial mass production. The obtained carbonaceous hybrid powder has stable structure, excellent performance, particularly good conductivity and good application prospect.
Drawings
The following drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain the invention, without limitation to the invention.
FIG. 1 is a flow chart of a process for preparing a carbonaceous hybrid powder according to an embodiment of the invention;
FIG. 2 is a schematic view of the microstructure of a carbonaceous hybrid powder according to an embodiment of the invention;
FIG. 3 is an X-ray photoelectron spectrum of the carbonaceous hybrid powder of example 1.
Wherein, the reference numerals are as follows:
100: one-dimensional carbon nanotubes
200: hybrid carbon sphere
300: zero-dimensional carbon material
Detailed Description
The following provides various embodiments or examples to enable those skilled in the art to practice the invention as described herein. These are, of course, merely examples and are not intended to limit the invention from that described. The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and should be considered as specifically disclosed herein.
Fig. 1 shows a process flow chart of preparing the carbonaceous hybrid powder according to an embodiment of the invention, and as shown in fig. 1, the preparation method of the carbonaceous hybrid powder comprises the following steps: dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion; mixing two-dimensional graphene oxide with a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion liquid, and performing solvent removal granulation on the second aqueous dispersion liquid to obtain hybridized carbon spheres; dispersing the hybridized carbon spheres in the first aqueous dispersion liquid to obtain a third aqueous dispersion liquid; and the third aqueous dispersion is dried, reduced and crushed to obtain the carbonaceous hybrid powder.
According to the invention, the carbon materials with different dimensions are compositely constructed, so that the structures and the properties of the carbon materials are complemented, the synergistic effect of the carbon materials is exerted to the greatest extent, and the carbon materials have better performance than any single carbon material. However, the existing method is complex in multiple processes, high in cost and not friendly to the environment, and the obtained product is low in carbon content and cannot meet the actual requirements.
The inventor of the present invention found that by hybridizing two-dimensional graphene oxide with a zero-dimensional carbon material, constructing a hybrid carbon material having a plurality of oxygen-containing functional groups such as carboxyl groups, quinone groups, epoxy groups and the like on the surface, and dispersing the hybrid carbon material in an aqueous dispersion liquid containing carbon nanotubes, a stably dispersed zero-dimensional carbon sphere and one-dimensional carbon nanotube hybrid aqueous composite dispersion liquid can be formed by electrostatic repulsion. The aqueous composite dispersion liquid is subjected to drying reduction treatment to obtain the carbonaceous hybrid powder which is stable in structure and contains a plurality of different types of carbon materials, and stacking and re-agglomeration of various carbon materials can be restrained by constructing the carbonaceous hybrid powder in a three-dimensional form, so that the carbonaceous hybrid powder has more excellent performance. In addition, the preparation process of the carbonaceous hybrid powder is carried out in an aqueous system, so that solvents such as a surfactant and a binder are not needed, and the process flow is nontoxic and pollution-free and is suitable for industrial mass production.
Specifically, the following briefly describes the preparation process of the aforementioned carbonaceous hybrid powder.
First, one-dimensional carbon nanotubes are dispersed in water to obtain a first aqueous dispersion. The one-dimensional carbon nanotubes may be dispersed in water in one or more of an ultrasonic dispersion, a mechanical stirrer, a high-speed shear disperser, and a homogenizer. In the dispersing process of the carbon nano tube, not only can the van der Waals force among CNTs be weakened, but also the dangling bond of the CNTs can be increased, thereby being beneficial to improving the dispersibility of the CNTs in water. In particular, the CNTs can also comprise carboxylated or hydroxylated CNTs, and after ultrasonic dispersion or mechanical stirring, dissociation of acid radical ions on the surface of the CNTs is facilitated, and the negative charge on the surface of the CNTs is increased, so that the dispersion stability of the CNTs aqueous dispersion liquid is improved. The carbon nanotubes may be single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), or a combination thereof, to which the present invention is not limited.
In some embodiments, the concentration of the first aqueous dispersion, i.e., the concentration of the one-dimensional carbon nanotubes in the first aqueous dispersion, is from 0.1mg/mL to 5mg/mL, e.g., 0.1mg/mL, 1.6mg/mL, 2mg/mL, 2.5mg/mL, 3mg/mL, 3.7mg/mL, 4mg/mL, 4.8mg/mL, 5mg/mL, etc. The length of the one-dimensional carbon nanotube is 1 μm to 20 μm, for example, 1 μm, 4 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 17 μm, 18 μm, 20 μm, etc.
Next, hybrid carbon spheres are prepared. The steps of preparing the hybrid carbon spheres and the steps of preparing the first aqueous dispersion liquid are not limited to the sequence, and the hybrid carbon spheres and the first aqueous dispersion liquid may be prepared first, and the invention is not limited thereto.
The preparation of the hybrid carbon sphere comprises the following steps: firstly mixing the two-dimensional graphene oxide with a zero-dimensional carbon material, dispersing in water to obtain a second aqueous dispersion liquid, and then further removing solvent from the second aqueous dispersion liquid for granulating to obtain the hybrid carbon spheres.
The zero-dimensional carbon material can be one or more of acetylene black, conductive carbon black (SP), ketjen black, carbon black, fullerene, carbon quantum dots and onion carbon. Graphene Oxide (GO) is a product of chemically oxidizing and peeling graphene powder, and has more active properties than graphene due to the increase of oxygen-containing functional groups thereon after oxidation, and can improve the properties thereof through various reactions with oxygen-containing functional groups. The graphene oxide has excellent dispersibility in water, and the introduction of the oxygen-containing groups not only enables the graphene oxide to have chemical stability, but also provides surface modification active positions and larger specific surface area for synthesizing graphene/graphene oxide materials.
In some embodiments, the aforementioned two-dimensional graphene oxide to zero-dimensional carbon material mass ratio is (1-10): (0.1-5), e.g., 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 2:1, 3:1, 4:1, 4:3, 5:2, 7:1, 10:1, etc. The concentration of the second aqueous dispersion, i.e., the concentration of the two-dimensional graphene oxide and the zero-dimensional carbon material in the second aqueous dispersion is 0.1mg/mL to 30mg/mL, for example, 0.1mg/mL, 1mg/mL, 3mg/mL, 5mg/mL, 7mg/mL, 10mg/mL, 13mg/mL, 14mg/mL, 16mg/mL, 20mg/mL, 22mg/mL, 25mg/mL, 27mg/mL, 29mg/mL, 30mg/mL, etc. The dispersion manner of the second aqueous dispersion may be one or more of ultrasonic dispersion, mechanical stirrer, high-speed shearing disperser and homogenizer, and the present invention is not limited thereto.
And removing solvent from the second aqueous dispersion liquid, and granulating to obtain the hybrid carbon spheres. The solvent removal granulation mode is carried out in a spray granulation mode, and compared with the mode of directly drying the second aqueous dispersion liquid, the agglomeration of graphene oxide can be effectively avoided. Specifically, the second aqueous dispersion is continuously granulated by a sprayer under the conditions of working temperature of 110-150 ℃, such as 110 ℃, 114 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃, 145 ℃, and the like, working pressure of 0.1-0.3 MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.26MPa, 0.3MPa, and the like, and working flow rate of 300-1800 mL/h, such as 300-400 mL/h, 450mL/h, 600mL/h, 700mL/h, 850mL/h, 900mL/h, 1200mL/h, 1300mL/h, 15000mL/h, 1700mL/h, and the like, to obtain the hybrid carbon spheres. The size of the hybrid carbon spheres may be adjusted according to the spray head of the sprayer, and in some embodiments, the resulting hybrid carbon spheres have a diameter of 500nm to 5 μm, e.g., 500nm, 1 μm, 3 μm, 5 μm, etc.
Further, after the first aqueous dispersion liquid and the hybridized carbon spheres are obtained, the hybridized carbon spheres with oxygen-containing functional groups on the surface are dispersed in the first aqueous dispersion liquid, and the stably dispersed zero-dimensional carbon spheres and one-dimensional carbon nanotube hybridized aqueous composite dispersion liquid, namely third aqueous dispersion liquid, can be formed through electrostatic repulsion, and the third aqueous dispersion liquid is dried, reduced and crushed to obtain the carbonaceous hybridized powder. FIG. 2 shows a schematic microstructure of a carbonaceous hybrid powder according to an embodiment of the invention. As can be seen from fig. 2, the carbonaceous hybrid powder includes the one-dimensional carbon nanotube 100 and the hybrid carbon sphere 200 attached thereto, wherein the hybrid carbon sphere 200 is further attached with the scattered zero-dimensional carbon material 300, and the whole material includes a plurality of different kinds of carbon materials, and by constructing in such a three-dimensional form, stacking and re-agglomeration of the various carbon materials can be suppressed, thereby making the obtained carbonaceous hybrid powder exhibit more excellent performance.
In some embodiments, the concentration of the third aqueous dispersion is from 0.1mg/mL to 50mg/mL, e.g., 0.1mg/mL, 2mg/mL, 3mg/mL, 5mg/mL, 7mg/mL, 11mg/mL, 12mg/mL, 14mg/mL, 17mg/mL, 20mg/mL, 23mg/mL, 25mg/mL, 27mg/mL, 29mg/mL, 30mg/mL, 35mg/mL, 40mg/mL, 45mg/mL, and the like. The mass ratio of the hybridized carbon spheres to the one-dimensional carbon nanotubes in the third aqueous dispersion is (1-10) (0.1-2), such as 1:0.1, 1:1, 1:2, 2:1, 3:1, 4:1, 5:2, 7:1, 10:1, and the like. The hybrid carbon spheres are dispersed in the first aqueous dispersion in a manner of low-speed magnetic stirring, the rotation speed of the low-speed magnetic stirring is 50rpm/min to 100rpm/min, such as 50rpm/min, 70rpm/min, 80rpm/min, 85rpm/min, 90rpm/min and the like, and the treatment time is 1min to 10min, such as 1min, 4min, 5min, 7min, 8min, 9min, 10min and the like.
Further, the drying mode of the third dispersion liquid may be freeze drying, the reduction mode includes high temperature thermal reduction under inert atmosphere, the crushing mode may be mechanical crushing, and the carbonaceous hybrid powder of the invention is obtained by sequentially drying, reducing and crushing the third dispersion liquid.
The invention will be further illustrated by the following examples, but the invention is not limited thereby. The reagents used in the present invention are commercially available unless otherwise specified.
Example 1
This example is a description of the method for preparing the carbonaceous hybrid powder of the invention.
1) Mixing 0.2g of SWCNT powder with 100mL of deionized water, and carrying out high-speed shearing dispersion for 1h and ultrasonic dispersion for 3h at the rotating speed of 10000rpm to prepare a uniformly dispersed carbon nano tube aqueous dispersion liquid with the concentration of 2 mg/mL.
2) Mixing 0.5g of graphene oxide powder, 0.1g of ketjen black and 150mL of deionized water, and magnetically stirring for 4 hours at the rotating speed of 500rpm to prepare a uniformly-dispersed 4mg/mL hybrid carbon material water-based dispersion. The hybrid carbon material aqueous dispersion liquid is continuously granulated by spraying equipment under the conditions of working pressure of 0.1MPa, working temperature of 110 ℃ and working flow rate of 500mL/h, so as to prepare the hybrid carbon ball.
3) And (3) mixing 2g of the obtained hybridized carbon spheres with the carbon nano tube aqueous dispersion liquid 1, and magnetically stirring for 1min at the rotating speed of 100rpm to obtain the hybridized carbon material aqueous dispersion liquid. And (3) pre-freezing the water-based dispersion liquid 3 for 3 hours, vacuum freeze-drying for 24 hours, then placing the water-based dispersion liquid in a vacuum tube furnace for high-temperature reduction at 800 ℃ for 2 hours, and finally carrying out pulverization treatment on a sample by a food processor to obtain the carbonaceous hybrid powder.
Fig. 3 is an X-ray photoelectron spectrum (XPS) of the carbonaceous hybrid powder of example 1, and it can be seen that the carbonaceous hybrid powder contains carbon and oxygen elements, indicating that graphene oxide is incorporated into the carbonaceous hybrid powder.
Example 2
This example is a description of the method for preparing the carbonaceous hybrid powder of the invention.
1) Mixing 0.1g of hydroxylated carbon nanotube powder with 100mL of deionized water, and carrying out high-speed shearing dispersion for 0.5h and ultrasonic dispersion for 2h at the rotating speed of 10000rpm to prepare a uniformly dispersed 1mg/mL carbon nanotube aqueous dispersion.
2) Mixing 0.6g of graphene oxide powder, 0.1g of ketjen black, 0.05g of acetylene black and 200mL of deionized water, and shearing at a high speed of 2000rpm for 1 hour to prepare a uniformly dispersed 3.75mg/mL hybrid carbon material aqueous dispersion. And (3) continuously granulating the hybrid carbon material water-based dispersion liquid through spraying equipment under the conditions that the working pressure is 0.3MPa, the working temperature is 120 ℃ and the working flow rate is 1000mL/h, so as to prepare the hybrid carbon spheres.
3) And (3) blending 4g of the obtained hybridized carbon spheres with the carbon nano tube aqueous dispersion liquid, and magnetically stirring for 2min at the rotating speed of 50rpm to obtain the hybridized carbon material aqueous dispersion liquid. And (3) pre-freezing the water-based dispersion liquid for 3 hours, vacuum freeze-drying for 24 hours, placing the water-based dispersion liquid in an inert atmosphere tube furnace, reducing the water-based dispersion liquid at a high temperature of 1000 ℃ for 3 hours, and finally carrying out pulverization treatment on a sample by a ball mill to obtain the carbonaceous hybrid powder.
Example 3
This example is a description of the method for preparing the carbonaceous hybrid powder of the invention.
1) Mixing 0.5g of carboxylated carbon nanotube powder with 200mL of deionized water, and carrying out high-speed shearing dispersion for 0.5h and ultrasonic dispersion for 2h under the condition of rotating speed of 10000rpm to prepare a uniformly dispersed carbon nanotube aqueous dispersion liquid of 2.5 mg/mL.
2) 2g of graphene oxide powder, 0.2g of SP and 500mL of deionized water are taken and mixed, and high-speed shearing is carried out for 1h under the condition of 2000rpm, so as to prepare 4.4mg/mL of uniformly dispersed hybrid carbon material aqueous dispersion liquid. And continuously granulating the hybrid carbon material water-based dispersion liquid through spraying equipment under the conditions that the working pressure is 0.3MPa, the working temperature is 110 ℃ and the working flow rate is 1200mL/h, so as to prepare the hybrid carbon spheres.
3) And (3) blending 4g of the obtained hybridized carbon spheres with the carbon nano tube aqueous dispersion liquid, and magnetically stirring for 1min at the rotating speed of 60rpm to obtain the hybridized carbon material aqueous dispersion liquid. And (3) pre-freezing the water-based dispersion liquid for 3 hours, vacuum freeze-drying for 24 hours, placing the water-based dispersion liquid in an inert atmosphere tube furnace, reducing the water-based dispersion liquid at a high temperature of 1100 ℃ for 3 hours, and finally carrying out pulverization treatment on a sample by a food processor to obtain the carbonaceous hybrid powder.
Comparative example 1
1) Mixing 0.5g of carboxylated carbon nanotube powder with 200mL of deionized water, and carrying out high-speed shearing dispersion for 1h and ultrasonic dispersion for 0.5h under the condition of rotating speed of 10000rpm to prepare a uniformly dispersed carbon nanotube aqueous dispersion liquid of 2.5 mg/mL.
2) 4g of zero-dimensional SP powder is taken to be mixed with the carbon nano tube aqueous dispersion liquid, and the magnetic stirring is carried out for 1min under the condition of the rotating speed of 60rpm, so as to obtain the hybrid carbon material aqueous dispersion liquid. And (3) pre-freezing the water-based dispersion liquid for 3 hours, vacuum freeze-drying for 24 hours, placing the water-based dispersion liquid in an inert atmosphere tube furnace, reducing the water-based dispersion liquid at a high temperature of 1100 ℃ for 3 hours, and finally carrying out pulverization treatment on a sample by a food processor to obtain the carbonaceous hybrid powder.
Test example 1
The materials obtained in examples 1 to 3 and comparative example 1 were subjected to a powder conductivity test. Wherein, the powder conductivity test adopts a ST2722-SZ type semiconductor powder resistivity tester. The depth of each feeding cavity is ensured to be 10mm, the test pressure is 18MPa, the conductivity result is calculated, and the sample of each embodiment is tested for 3 times and averaged. The test results are shown in Table 1 below.
TABLE 1
| Conductivity S/m | |
| Example 1 | 6583 |
| Example 2 | 6302 |
| Example 3 | 6891 |
| Comparative example 1 | 3256 |
As can be seen from Table 1, the carbonaceous hybrid powder prepared by the method of the invention has conductivity reaching 6000S/m or more and excellent conductivity. Therefore, the method for preparing the carbonaceous hybrid powder has the advantages of simple process, environmental protection and no pollution, and the obtained carbonaceous hybrid powder has stable structure, excellent conductivity and good application prospect.
It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.
Claims (8)
1. The preparation method of the carbonaceous hybrid powder is characterized by comprising the following steps:
dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion;
mixing two-dimensional graphene oxide with a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion liquid, and performing solvent removal granulation on the second aqueous dispersion liquid to obtain hybridized carbon spheres;
the hybridized carbon spheres are dispersed in the first aqueous dispersion liquid to obtain a third aqueous dispersion liquid; a kind of electronic device with high-pressure air-conditioning system
The third dispersion liquid is subjected to freeze drying, thermal reduction and mechanical crushing in sequence to obtain the carbonaceous hybrid powder;
the mass ratio of the two-dimensional graphene oxide to the zero-dimensional carbon material in the second aqueous dispersion liquid is (1-10) (0.1-5), and the mass ratio of the hybrid carbon spheres to the one-dimensional carbon nanotubes in the third aqueous dispersion liquid is (1-10) (0.1-2);
the solvent removal granulation is carried out in a spray granulation mode, the working temperature of the spray granulation is 110-150 ℃, the working pressure is 0.1-0.3 MPa, and the working flow rate is 300-1800 mL/h.
2. The method of claim 1, wherein the one-dimensional carbon nanotubes are selected from one or more of carbon nanotubes, hydroxylated carbon nanotubes, and carboxylated carbon nanotubes, the carbon nanotubes comprising single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
3. The method of claim 1, wherein the concentration of the first aqueous dispersion is 0.1mg/mL to 5mg/mL; the concentration of the second aqueous dispersion liquid is 0.1 mg/mL-30 mg/mL; the concentration of the third aqueous dispersion liquid is 0.1 mg/mL-50 mg/mL.
4. The preparation method of claim 1, wherein the length of the one-dimensional carbon nanotubes is 1-20 [ mu ] m, and the diameter of the hybrid carbon spheres is 500-5 [ mu ] m.
5. The method of claim 1, wherein the zero-dimensional carbon material is selected from one or more of acetylene black, ketjen black, fullerenes, carbon quantum dots, and onion carbon.
6. The method of claim 1, wherein the zero-dimensional carbon material is carbon black.
7. The preparation method of claim 1, wherein the hybrid carbon spheres are dispersed in the first aqueous dispersion in a low-speed magnetic stirring manner, the rotation speed of the low-speed magnetic stirring is 50 rpm/min-100 rpm/min, and the treatment time is 1 min-10 min.
8. The method of claim 1, wherein the first aqueous dispersion and the second aqueous dispersion are each independently selected from one or more of ultrasonic dispersion, mechanical stirrer, high-speed shear disperser, and homogenizer.
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