CN111470491A - Carbon hybrid powder and preparation method thereof - Google Patents
Carbon hybrid powder and preparation method thereof Download PDFInfo
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- CN111470491A CN111470491A CN202010284190.XA CN202010284190A CN111470491A CN 111470491 A CN111470491 A CN 111470491A CN 202010284190 A CN202010284190 A CN 202010284190A CN 111470491 A CN111470491 A CN 111470491A
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Abstract
The invention provides a carbonaceous hybrid powder and a preparation method thereof, and the method comprises the following steps: dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion liquid; mixing two-dimensional graphene oxide and a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion solution, and removing a solvent from the second aqueous dispersion solution for granulation to obtain hybrid carbon spheres; dispersing the hybrid carbon spheres in the first aqueous dispersion to obtain a third aqueous dispersion; and drying, reducing and crushing the third aqueous dispersion liquid to obtain the carbonaceous hybrid powder. The method has the advantages of simple process, environmental protection, no pollution, suitability for industrial scale production, stable structure of the obtained carbon hybrid powder, excellent performance and good 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 excellent thermal and electrical conductivity, and the like, and thus is widely used in low-end fields such as electrodes, brushes, coke iron making, and the like in the early years. Since Andre geom and Konstantin Novoselov stripped graphene through scotch tape in 2014, various carbon materials have been expected to be more. These carbon materials include zero-dimensional carbon black, acetylene black, ketjen black, conductive carbon black (SP), onion carbon, fullerene, carbon quantum dots, one-dimensional carbon nanotubes, carbon fibers, two-dimensional graphene, graphdiyne, multilayer graphite nano-films, and three-dimensional graphite, carbon aerogel, graphene foam, and the like.
These carbon materials, when used alone, are somewhat self-limiting. If graphene is used as a lithium battery conductive agent alone, a large lamellar structure of the graphene can hinder transmission of lithium ions to a certain extent, so that an effective conductive network is constructed by adopting a graphene/carbon nanotube hybrid structure or a graphene/carbon black hybrid structure at present. The use of carbon black/carbon fiber hybrid materials in rubber systems is more beneficial to improving the mechanical properties of the rubber than if carbon black is used alone in rubber systems. Through the composite construction of carbon materials with different dimensions, the structures and properties of the carbon materials can be complemented, so that the synergistic effect of the carbon materials is exerted to the maximum 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 about the composite construction of a zero-dimensional carbon material and a same-dimensional carbon material are reported. For example, chinese patent CN104282914A discloses a powder conductive agent for lithium-sulfur battery, which is obtained by adding acetylene black and ball-milled carbon fibers into an ethanol solution for ultrasonic dispersion, and is used in a sulfur positive electrode to facilitate formation of a good conductive network, improve the conductivity of the positive electrode material, and further improve the discharge capacity of the battery. However, the composite carbon material obtained by the method is unstable in structure, and acetylene black and carbon fibers are not well combined. Chinese patent CN 108047495a discloses a super-strong composite material for in-situ synthesis of carbon nanotubes and carbon black, which has a perfect grape string-like structure with carbon nanotubes as main lines and generated carbon black particles as beads. However, the temperature required by the in-situ preparation method is as high as 1400-1700 ℃, and the required cost is high, so that the industrial application of the in-situ preparation 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 then blending zero-dimensional carbon black and the one-dimensional carbon fiber/gas phase carbon tube composite powder through a resin binder, a dispersant, a leveling agent, an anti-settling agent and a water repellent agent. However, this method requires various solvents such as a binder and further affects the carbon content of the material.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention mainly aims to overcome at least one defect in the prior art, and provides a preparation method of carbon hybrid powder and the obtained carbon hybrid powder so as to solve the problems of complex process, high cost, environmental friendliness, low quality of obtained products and the like of the existing method for compositely constructing the zero-dimensional carbon material and the same-dimensional carbon material.
In order to achieve the purpose, the 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 liquid; mixing two-dimensional graphene oxide and a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion solution, and removing a solvent from the second aqueous dispersion solution for granulation to obtain hybrid carbon spheres; dispersing the hybrid carbon spheres in the first aqueous dispersion to obtain a third aqueous dispersion; and drying, reducing and crushing the third aqueous dispersion liquid to obtain the carbon hybrid powder.
According to one embodiment of the present invention, the one-dimensional carbon nanotubes are selected from one or more of carbon nanotubes, including single-walled carbon nanotubes and/or multi-walled carbon nanotubes, hydroxylated carbon nanotubes and carboxylated carbon nanotubes.
According to one embodiment of the invention, the concentration of the first aqueous dispersion is 0.1mg/m L-5 mg/m L, the concentration of the second aqueous dispersion is 0.1mg/m L-30 mg/m L, the mass ratio of the two-dimensional graphene oxide to the zero-dimensional carbon material in the second aqueous dispersion is (1-10): 0.1-5), the concentration of the third aqueous dispersion is 0.1mg/m L-50 mg/m L, and the mass ratio of the hybrid carbon spheres to the one-dimensional carbon nanotubes in the third aqueous dispersion 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 an embodiment of the present invention, the zero-dimensional carbon material is selected from one or more of acetylene black, conductive carbon black, ketjen black, carbon black, fullerene, carbon quantum dot, and onion carbon.
According to one embodiment of the invention, the solvent-removing granulation is carried out by spray granulation, wherein 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 300m L/h-1800 m L/h.
According to one embodiment of the present invention, the mode of dispersing the hybrid carbon spheres in the first aqueous dispersion is low-speed magnetic stirring, the rotation speed of the low-speed magnetic stirring is 50rpm/min to 100rpm/min, and the treatment time is 1min to 10 min.
According to one embodiment of the present invention, the first aqueous dispersion and the second aqueous dispersion are dispersed in a manner each independently selected from one or more of ultrasonic dispersion, mechanical stirrer, high shear disperser and homogenizer.
According to an 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 obtained by adopting the preparation method.
According to the technical scheme, the invention has the beneficial effects that:
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 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 a water-based system, solvents such as surfactants, binders and the like are not needed, the process flow is non-toxic and pollution-free, and the method is suitable for industrial mass production. The obtained carbon hybrid powder has stable structure, excellent performance, especially good conductivity and good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a flow chart of a process for preparing a carbonaceous hybrid powder according to an embodiment of the present invention;
FIG. 2 is a schematic view of the microstructure of a carbonaceous hybrid powder according to an embodiment of the present invention;
FIG. 3 is an X-ray photoelectron spectrum of the carbonaceous hybrid powder of example 1.
Wherein the reference numbers are as follows:
100: one-dimensional carbon nanotube
200: hybrid carbon sphere
300: zero-dimensional carbon material
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Fig. 1 shows a flow chart of a process for preparing a carbonaceous hybrid powder according to an embodiment of the present invention, and as shown in fig. 1, the method for preparing the carbonaceous hybrid powder includes the following steps: dispersing one-dimensional carbon nanotubes in water to obtain a first aqueous dispersion liquid; mixing two-dimensional graphene oxide and a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion solution, and removing a solvent from the second aqueous dispersion solution for granulation to obtain hybrid carbon spheres; dispersing the hybrid carbon spheres in the first aqueous dispersion to obtain a third aqueous dispersion; and drying, reducing and crushing the third aqueous dispersion liquid to obtain the carbon hybrid powder.
According to the invention, through carrying out composite construction on carbon materials with different dimensions, the structures and properties of the carbon materials can be complemented, so that the synergistic effect of the carbon materials is exerted to the maximum extent, and the carbon materials show more excellent performance than any single carbon material. However, most of the existing methods have complex process, high cost and unfriendly environment, and the obtained product has low carbon content and cannot meet the actual requirement.
The inventor of the present invention found that a hybrid carbon material having various oxygen-containing functional groups such as carboxyl, quinonyl, epoxy and the like on the surface is constructed by hybridizing two-dimensional graphene oxide with a zero-dimensional carbon material, and is dispersed in an aqueous dispersion liquid containing carbon nanotubes, so that a stably dispersed aqueous composite dispersion liquid hybridized with zero-dimensional carbon spheres and one-dimensional carbon nanotubes can be formed by electrostatic repulsion. The aqueous composite dispersion liquid is dried and reduced to obtain carbonaceous hybrid powder which is stable in structure and contains various different types of carbon materials, and stacking and re-agglomeration of various carbon materials can be inhibited by constructing the carbonaceous hybrid powder in a three-dimensional form, so that more excellent performance is shown. In addition, the preparation process of the carbonaceous hybrid powder is carried out in an aqueous system, solvents such as surfactants, binders and the like are not needed, the process flow is nontoxic and pollution-free, and the preparation method is suitable for industrial mass production.
Specifically, the process for producing the carbonaceous hybrid powder will be briefly described below.
First, one-dimensional carbon nanotubes are dispersed in water to obtain a first aqueous dispersion. The manner of dispersing the one-dimensional carbon nanotubes in water may be one or more of ultrasonic dispersion, mechanical stirrer, high-speed shear disperser, and homogenizer. In the dispersion process of the carbon nano tube, the van der Waals force between the CNTs can be weakened, the dangling bond of the CNTs can be increased, and the improvement of the dispersibility of the CNTs in water is facilitated. In particular, the selected CNTs can further comprise carboxylated or hydroxylated CNTs, and after the CNTs are subjected to ultrasonic dispersion or mechanical stirring, the dissociation of acid radical ions on the surface of the CNTs is facilitated, and the negative charges on the surface of the CNTs are increased, so that the dispersion stability of the aqueous CNTs 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 0.1mg/m L to 5mg/m L, such as 0.1mg/m L0, 1.6mg/m L, 2mg/m L, 2.5mg/m L, 3mg/m L, 3.7mg/m L, 4mg/m L, 4.8mg/m L, 5mg/m L, etc. the length of the one-dimensional carbon nanotubes is 1 μm to 20 μm, such as 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 were prepared. It should be noted that, the steps of preparing the hybrid carbon spheres and the steps of preparing the first aqueous dispersion liquid are not limited to a sequential order, and the hybrid carbon spheres may be prepared first and then the first aqueous dispersion liquid may be prepared, but the invention is not limited thereto.
The preparation of the hybrid carbon sphere comprises the following steps: mixing two-dimensional graphene oxide and a zero-dimensional carbon material, dispersing in water to obtain a second aqueous dispersion solution, and then further removing a solvent from the second aqueous dispersion solution for granulation to obtain the hybrid carbon spheres.
Wherein the zero-dimensional carbon material may be one or more of acetylene black, conductive carbon black (SP), Ketjen black, carbon black, fullerene, carbon quantum dot, and onion carbon. Graphene Oxide (GO) is a product of graphene powder after chemical oxidation and exfoliation, and has more active properties than graphene due to the increase of oxygen-containing functional groups after oxidation, and can improve the properties of graphene through various reactions with the oxygen-containing functional groups. The graphene oxide has excellent dispersibility in water, and the introduction of the oxygen-containing group not only enables the graphene oxide to have chemical stability, but also provides a surface modification active site and a larger specific surface area for synthesizing the graphene-based/graphene oxide-based material.
In some embodiments, the mass ratio of the two-dimensional graphene oxide to the zero-dimensional carbon material is (1-10): (0.1-5), for example, 1:0.1, 1:1, 1:2, 1:3, 1:4, 1:5, 2:1, 3:1, 4:3, 5:2, 7:1, 10:1, etc. the concentration of the second aqueous dispersion, that is, the concentration of the two-dimensional graphene oxide and the zero-dimensional carbon material in the second aqueous dispersion is 0.1mg/m L-30 mg/m L, for example, 0.1mg/m L, 1mg/m L, 3mg/m L, 5mg/m L, 7mg/m 7374, 10mg/m L, 13mg/m L, 14mg/m L, 16mg/m L, 20mg/m L, 22mg/m L, 25mg/m 3837, 25mg/m 3937 mg/m, 9634 mg/m, 9638 mg/m of the second aqueous dispersion may be obtained by a mechanical homogenizer, or other methods.
The second aqueous dispersion is subjected to desolventizing granulation to obtain hybrid carbon spheres, wherein the desolventizing granulation is performed by spray granulation, and agglomeration of graphene oxide can be effectively avoided compared with direct drying of the second aqueous dispersion, and specifically, the second aqueous dispersion is subjected to a sprayer at a working temperature of 110 ℃ to 150 ℃, such as 110 ℃, 114 ℃, 120 ℃, 125 ℃, 130 ℃, 140 ℃, 145 ℃ and the like, at a working pressure of 0.1MPa to 0.3MPa, such as 0.1MPa, 0.15MPa, 0.2MPa, 0.26MPa, 0.3MPa and the like, at a working flow rate of 300m L/h to 1800m L/h, such as 300m L0/h, 400m L1/h, 450m L2/h, 600m L/h, 700m L/h, 850m L/h, 900m L/h, 1200m L/h, 1300m L/h, 15000m L/h, 1700m L/h and the like, and the size of the hybrid carbon spheres obtained by continuous spray nozzle can be adjusted to 500 μm, such as the size of the hybrid carbon spheres obtained in the example, and the size of the spray nozzle can be adjusted according to 500 μm, and the conditions of the obtained hybrid carbon spheres can be adjusted according to 500 μm.
Further, after the first aqueous dispersion liquid and the hybrid carbon spheres are obtained, the hybrid carbon spheres with oxygen-containing functional groups on the surfaces are dispersed in the first aqueous dispersion liquid, and a stably dispersed aqueous composite dispersion liquid of the hybridization of the zero-dimensional carbon spheres and the one-dimensional carbon nanotubes, namely a 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 hybrid powder. Fig. 2 shows a schematic microstructure of the carbonaceous hybrid powder according to an embodiment of the present invention. As can be seen from fig. 2, the carbonaceous hybrid powder comprises one-dimensional carbon nanotubes 100 and hybrid carbon spheres 200 attached thereto, wherein the hybrid carbon spheres 200 are further attached with scattered zero-dimensional carbon materials 300, the whole material comprises a plurality of different types of carbon materials, and the three-dimensional construction can inhibit stacking and re-agglomeration of the carbon materials, so that the obtained carbonaceous hybrid powder shows more excellent performance.
In some embodiments, the third aqueous dispersion has a concentration of 0.1mg/m L-50 mg/m L, e.g., 0.1mg/m L0, 2mg/m L1, 3mg/m L2, 5mg/m L3, 7mg/m L4, 11mg/m L5, 12mg/m L6, 14mg/m L7, 17mg/m L8, 20mg/m L9, 23mg/m L, 25mg/m L, 27mg/m L, 29mg/m L, 30mg/m L, 35mg/m L, 40mg/m L, 45mg/m L, etc., the mass ratio of the hybrid carbon spheres to the one-dimensional carbon nanotubes in the third aqueous dispersion is (1-10), e.g., 1: 0.1-2, e.g., 1:0.1, 1:1, 2:1, 3: 4: 1min, 1: 5min, 1: 10: 5: 10min, 5: 10: 5: 1: 10, 5: 10, 5: 7: 5: 1, 5: 10: 5: 1, 5: 10: 5: 1, 5: 1, 5: 1, 5: 10: 5: 1, 5: 10:1, 5.
Further, the drying method of the third dispersion liquid may be freeze drying, the reduction method includes performing high-temperature thermal reduction in an inert atmosphere, the pulverization method may be mechanical pulverization, and the carbonaceous hybrid powder of the present invention is obtained by sequentially drying, reducing and pulverizing the third dispersion liquid.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, the reagents used in the present invention are commercially available.
Example 1
This example is intended to illustrate the method for producing a carbonaceous hybrid powder according to the present invention.
1) 0.2g of SWCNT powder and 100ml of deionized water are mixed, and high-speed shearing dispersion for 1h and ultrasonic dispersion for 3h are carried out under the condition that the rotating speed is 10000rpm to prepare the carbon nano tube aqueous dispersion liquid with uniformly dispersed 2mg/m L.
2) 0.5g of graphene oxide powder, 0.1g of Ketjen black and 150ml of deionized water are mixed, magnetic stirring is carried out for 4h under the condition that the rotating speed is 500rpm, and uniformly dispersed water-based dispersion liquid of the hybrid carbon material with the concentration of 4mg/m L is prepared, and the water-based dispersion liquid of the hybrid carbon material is continuously granulated through spraying equipment under the conditions that the working pressure is 0.1MPa, the working temperature is 110 ℃ and the working flow rate is 500m L/h, so that the hybrid carbon ball is prepared.
3) And (3) mixing 2g of the prepared hybrid carbon spheres with the carbon nanotube aqueous dispersion liquid 1, and performing magnetic stirring for 1min at the rotating speed of 100rpm to obtain the hybrid carbon material aqueous dispersion liquid. And (3) pre-freezing the aqueous dispersion liquid 3 for 3 hours and freeze-drying the aqueous dispersion liquid in vacuum for 24 hours, then placing the aqueous dispersion liquid in a vacuum tube furnace for high-temperature reduction at 800 ℃ for 2 hours, and finally performing pulverization treatment on a sample by a food processor to obtain the carbonaceous hybrid powder.
Fig. 3 is an X-ray photoelectron spectroscopy (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 intended to illustrate the method for producing a carbonaceous hybrid powder according to the present invention.
1) 0.1g of hydroxylated carbon nanotube powder is mixed with 100ml of deionized water, and the mixture is subjected to high-speed shearing dispersion for 0.5h and ultrasonic dispersion for 2h under the condition that the rotating speed is 10000rpm to prepare a uniformly dispersed 1mg/m L carbon nanotube aqueous dispersion liquid.
2) 0.6g of graphene oxide powder, 0.1g of Ketjen black, 0.05g of acetylene black and 200ml of deionized water are mixed, high-speed shearing is carried out for 1h under the condition of 2000rpm of rotation speed, and uniformly dispersed hybrid carbon material water-based dispersion liquid with the concentration of 3.75mg/m L is prepared.
3) And (3) mixing 4g of the prepared hybrid carbon spheres with the aqueous dispersion liquid of the carbon nano tubes, and magnetically stirring for 2min at the rotating speed of 50rpm to obtain the aqueous dispersion liquid of the hybrid carbon material. And pre-freezing the aqueous dispersion liquid for 3h, vacuum freeze-drying for 24h, then placing the aqueous dispersion liquid in an inert atmosphere tubular furnace for high-temperature reduction for 3h at 1000 ℃, and finally performing pulverization treatment on the sample by a ball mill to obtain the carbonaceous hybrid powder.
Example 3
This example is intended to illustrate the method for producing a carbonaceous hybrid powder according to the present invention.
1) 0.5g of carboxylated carbon nanotube powder is mixed with 200ml of deionized water, and the mixture is subjected to high-speed shearing dispersion for 0.5h and ultrasonic dispersion for 2h under the condition that the rotating speed is 10000rpm to prepare a uniformly dispersed 2.5mg/m L carbon nanotube aqueous dispersion liquid.
2) 2g of graphene oxide powder, 0.2g of SP and 500ml of deionized water are mixed, high-speed shearing is carried out for 1h under the condition that the rotating speed is 2000rpm, and uniformly dispersed 4.4mg/m L hybrid carbon material water system dispersion liquid is prepared, and the hybrid carbon material water system dispersion liquid is continuously granulated through spraying equipment under the conditions that the working pressure is 0.3MPa, the working temperature is 110 ℃ and the working flow rate is 1200m L/h, so that the hybrid carbon ball is prepared.
3) And (3) mixing 4g of the prepared hybrid carbon spheres with the aqueous dispersion liquid of the carbon nano tubes, and magnetically stirring for 1min at the rotating speed of 60rpm to obtain the aqueous dispersion liquid of the hybrid carbon material. And pre-freezing the aqueous dispersion liquid for 3h, vacuum freeze-drying for 24h, then placing the aqueous dispersion liquid in an inert atmosphere tube furnace for high-temperature reduction at 1100 ℃ for 3h, and finally performing pulverization treatment on the sample through a food processor to obtain the carbonaceous hybrid powder.
Comparative example 1
1) 0.5g of carboxylated carbon nanotube powder is mixed with 200ml of deionized water, and the mixture is subjected to high-speed shearing dispersion for 1 hour and ultrasonic dispersion for 0.5 hour under the condition that the rotating speed is 10000rpm to prepare a uniformly dispersed 2.5mg/m L carbon nanotube aqueous dispersion liquid.
2) And (3) mixing 4g of zero-dimensional SP powder with the aqueous dispersion liquid of the carbon nano tube, and magnetically stirring for 1min at the rotating speed of 60rpm to obtain the aqueous dispersion liquid of the hybrid carbon material. And pre-freezing the aqueous dispersion liquid for 3h, vacuum freeze-drying for 24h, then placing the aqueous dispersion liquid in an inert atmosphere tube furnace for high-temperature reduction at 1100 ℃ for 3h, and finally performing pulverization treatment on the sample through 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 an ST2722-SZ type semiconductor powder resistivity tester. The conductivity results were calculated by ensuring that the depth of the feeding chamber was 10mm each time and the test pressure was 18MPa, and the average value was taken 3 times for each example sample. 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 carbon hybrid powder prepared by the method of the invention has the conductivity of more than 6000S/m and excellent conductivity. Therefore, the method for preparing the carbon hybrid powder has the advantages of simple process, environmental protection and no pollution, and the obtained carbon hybrid powder has stable structure, shows excellent conductivity and has good application prospect.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (10)
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 liquid;
mixing two-dimensional graphene oxide and a zero-dimensional carbon material, dispersing the mixture in water to obtain a second aqueous dispersion solution, and removing a solvent from the second aqueous dispersion solution for granulation to obtain hybrid carbon spheres;
dispersing the hybrid carbon spheres in the first aqueous dispersion to obtain a third aqueous dispersion; and
and drying, reducing and crushing the third aqueous dispersion liquid to obtain the carbonaceous hybrid powder.
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, and the carbon nanotubes comprise single-walled carbon nanotubes and/or multi-walled carbon nanotubes.
3. The preparation method of claim 1, wherein the concentration of the first aqueous dispersion is 0.1mg/m L-5 mg/m L, the concentration of the second aqueous dispersion is 0.1mg/m L-30 mg/m L, the mass ratio of the two-dimensional graphene oxide to the zero-dimensional carbon material in the second aqueous dispersion is (1-10): 0.1-5), the concentration of the third aqueous dispersion is 0.1mg/m L-50 mg/m L, and the mass ratio of the hybrid carbon spheres to the one-dimensional carbon nanotubes in the third aqueous dispersion is (1-10): 0.1-2).
4. The method of claim 1, wherein 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.
5. The method according to claim 1, wherein the zero-dimensional carbon material is one or more selected from acetylene black, conductive carbon black, ketjen black, carbon black, fullerene, carbon quantum dot, and onion carbon.
6. The preparation method of claim 1, wherein the desolventizing granulation is performed by spray granulation, the spray granulation has a working temperature of 110 ℃ to 150 ℃, a working pressure of 0.1MPa to 0.3MPa, and a working flow rate of 300m L/h to 1800m L/h.
7. The preparation method according to claim 1, wherein the mode of dispersing the hybrid carbon spheres in the first aqueous dispersion liquid is low-speed magnetic stirring, the rotation speed of the low-speed magnetic stirring is 50rpm/min to 100rpm/min, and the treatment time is 1min to 10 min.
8. The method according to claim 1, wherein the first aqueous dispersion and the second aqueous dispersion are dispersed in a manner independently selected from one or more of ultrasonic dispersion, mechanical stirrer, high-speed shear disperser, and homogenizer.
9. The preparation method of claim 1, wherein the third dispersion is subjected to freeze drying, thermal reduction and mechanical pulverization in sequence to obtain the carbonaceous hybrid powder.
10. A carbonaceous hybrid powder obtained by the preparation method according to any one of claims 1 to 9.
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| CN114057190A (en) * | 2020-08-04 | 2022-02-18 | 北京石墨烯研究院 | Catalyst carrier carbon material for preparing carbon nano tube and preparation method and application thereof |
| CN114665096A (en) * | 2022-04-07 | 2022-06-24 | 湖南金阳烯碳新材料有限公司 | Graphene composite conductive slurry for battery and preparation method and application thereof |
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