CN109867275B - Method for preparing carbon nano onion by vacuum ball milling - Google Patents
Method for preparing carbon nano onion by vacuum ball milling Download PDFInfo
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- CN109867275B CN109867275B CN201910180452.5A CN201910180452A CN109867275B CN 109867275 B CN109867275 B CN 109867275B CN 201910180452 A CN201910180452 A CN 201910180452A CN 109867275 B CN109867275 B CN 109867275B
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Abstract
The invention relates to the technical field of carbon materials, in particular to a preparation method of carbon nano onions, which comprises the following steps: and under the vacuum condition, ball-milling the hydrocarbon polymer to obtain the carbon nano onion. The preparation method is simple and easy to implement, has good repeatability, and does not need harsh conditions such as high temperature, catalysts and the like; under the vacuum condition, the interaction between the hydrocarbon polymer and the ceramic ball leads the dissociation of C-H bond to generate hydrogen and a large number of short carbon chain free radicals, the newly formed free radicals are bonded again on a contact interface to form a stable aromatic carbon ring, and carbon nano onion is formed under the action of shearing force; the carbon nano onion prepared by the preparation method has good quality and high purity. According to the description of the embodiment, the carbon nano onion prepared by the method presents a multilayer graphene coiled structure, and the distance between the shells of the graphene is about 0.34 nm.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a method for preparing carbon nano onions by vacuum ball milling.
Background
Carbon Nano Onions (CNOs) are a novel zero-dimensional carbon nano material consisting of quasi-spherical or polyhedral graphite-like shell carbon materials. The nano-composite material has the characteristics of large specific surface area, closed stable structure, high thermal stability and the like, and has wide potential application value in the fields of electromagnetic shielding, gas or energy storage, ultra-high power micron-sized super capacitors, solid lubricants, lithium ion battery electrode materials, fuel cells, multi-phase catalysis, biocompatible nanocapsules for drug delivery systems and the like, so that the nano-composite material is more and more intensively concerned.
Since carbon nano onions were first discovered in 1980, the preparation method thereof mainly focused on arc discharge, electron beam irradiation, plasma method, nano-diamond vacuum heat treatment, organic metal polymer pyrolysis method or laser irradiation method. In recent years, new methods for preparing CNOs, such as burning naphthalene, carbonizing wood, or hydrothermal reaction, have been discovered. However, the CNOs prepared by the method has low quality and poor purity, and is difficult to meet the requirements of scientific research and application.
Disclosure of Invention
The invention aims to provide a preparation method of carbon nano onions, and the carbon nano onions prepared by the preparation method are high in quality and purity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of carbon nano onions, which comprises the following steps:
and under the vacuum condition, ball-milling the hydrocarbon polymer to obtain the carbon nano onion.
Preferably, the particle size of the hydrocarbon polymer is 10-100 nm.
Preferably, the hydrocarbon polymer is one or more of polyethylene, polypropylene and polystyrene.
Preferably, the ball milling temperature is 150-250 ℃.
Preferably, the rotation speed of the ball milling is 400-2000 r/min, and the ball milling time is 2-4 hours.
Preferably, the ball-milling ball-material ratio is (80-120): 1.
preferably, the grinding balls for ball milling are ceramic balls;
the ceramic balls are aluminum oxide ceramic balls, zirconium oxide ceramic balls or silicon nitride ceramic balls.
Preferably, the diameter of the grinding ball for ball milling is 3-12 mm.
Preferably, the vacuum degree of the vacuum is less than or equal to 1.0 multiplied by 10-2Pa。
The invention provides a preparation method of carbon nano onions, which comprises the following steps: and under the vacuum condition, ball-milling the hydrocarbon polymer to obtain the carbon nano onion. The preparation method is simple and easy to implement, has good repeatability, and does not need harsh conditions such as high temperature, catalysts and the like; under the vacuum condition, the interaction between the hydrocarbon polymer and the material ball leads C-H bond to be dissociated to generate hydrogen and a large number of short carbon chain free radicals, the newly formed free radicals are bonded on a contact interface again to form a stable aromatic carbon ring, and carbon nano-onions are formed under the action of shearing force; the carbon nano onion prepared by the preparation method has good quality and high purity. According to the description of the embodiment, the carbon nano onion prepared by the method presents a multilayer graphene coiled structure, and the distance between the shells of the graphene is about 0.34 nm.
Drawings
FIG. 1 is a low power transmission electron micrograph of a carbon nano-onion prepared by example 1;
FIG. 2 is a high-resolution transmission electron micrograph of a carbon nano-onion prepared in example 1;
fig. 3 is an EDX spectrum of a carbon nano-onion prepared by example 1.
Detailed Description
The invention provides a preparation method of carbon nano onions, which comprises the following steps:
and under the vacuum condition, ball-milling the hydrocarbon polymer to obtain the carbon nano onion.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the particle size of the hydrocarbon polymer is preferably 10-100 nm, more preferably 20-80 nm, and most preferably 40-60 nm; the hydrocarbon polymer is preferably one or more of polyethylene, polypropylene and polystyrene; when the hydrocarbon polymer is more than two of the specific choices, the proportion of the specific substances is not limited in any way, and the specific substances can be mixed according to any proportion.
In the present invention, the degree of vacuum of the vacuum is preferably 1.0X 10 or less-2Pa, more preferably ≤ 5.0 × 10-3Pa, most preferably ≤ 1.0 × 10-3Pa。
In the invention, the ball milling temperature is preferably 150-250 ℃, and more preferably 180-220 ℃; the rotation speed of the ball milling is preferably 400-2000 r/min, more preferably 500-1500 r/min, and most preferably 800-1200 r/min; the time for ball milling is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, and most preferably 3 hours.
In the invention, the ball-to-material ratio of the ball milling is preferably (80-120): 1, more preferably (90-110): 1; the grinding balls for ball milling are preferably ceramic balls; the ceramic balls are preferably alumina ceramic balls, zirconia ceramic balls or silicon nitride ceramic balls. In the invention, the diameter of the grinding ball for ball milling is preferably 3-12 mm; in the invention, the grinding ball can be a grinding ball with a single diameter or a mixed grinding ball with different diameters; the mixed grinding balls with different diameters are preferably large grinding balls with the diameter of 6-12 mm and small grinding balls with the diameter of 3-5 mm; the proportion of the large grinding ball and the small grinding ball is not limited in any way, and the grinding balls can be mixed according to any proportion.
In the invention, the ball milling can further promote the dissociation of C-H bonds in the hydrocarbon polymer to form a large number of aromatic carbon rings, which is beneficial to the formation of carbon nano-onions.
In the present invention, the ball milling is preferably performed in a ball mill.
In the invention, the preparation process of the carbon nano onion specifically comprises the following steps:
putting hydrocarbon polymer and grinding balls into a ball milling tank of a ball mill;
and (4) sequentially carrying out vacuumizing and heating treatment on the ball milling tank, setting ball milling parameters, and carrying out ball milling.
In the invention, the heating treatment can ensure that the ball milling is carried out within the temperature range of 150-250 ℃.
After the ball milling is finished, the obtained product is preferably cooled; the cooling method is not limited in any way, and the cooling method known to those skilled in the art can be adopted to cool the mixture to room temperature.
In the invention, the particle size of the carbon nano-onion prepared by the preparation method is 10-100 nm, and the distance between graphene shells is 0.34-0.40 nm.
The following will explain the preparation method of carbon nano-onion provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
According to the proportion of 90:1, polyethylene with the particle size of 10-100 nm and aluminum oxide ceramic balls with the diameter of 6mm are placed in a ball milling tank, and the ball milling tank is vacuumized to 1.0 multiplied by 10-2And Pa, heating the ball milling tank to 200 ℃, carrying out ball milling (the rotating speed of the ball milling is 400 r/min, the ball milling time is 3 hours), and cooling to room temperature to obtain the carbon nano onion.
The carbon nano onions are subjected to TEM test, the test results are shown in figures 1 and 2, and the test results show that the particle size distribution of the carbon nano onions is within the range of 10-100 nm, the carbon nano onions exhibit the structural characteristic of multilayer graphene curling, and the distance between graphene shell layers is 0.34 nm.
Fig. 3 is an EDX spectrum of the carbon nano onion, and it can be seen from the graph that the carbon nano onion mostly contains carbon elements except a small amount of oxygen elements, and the specification purity is high.
Example 2
According to the ball-material ratio of 100:1, polypropylene with the particle size of 20-80 nm and zirconia ceramic balls with the diameter of 12mm are placed in a ball-milling tank, and the ball-milling tank is vacuumized to 5.0 multiplied by 10-3And Pa, heating the ball milling tank to 200 ℃, carrying out ball milling (the rotating speed of the ball milling is 1000 r/min, the ball milling time is 3 hours), and cooling to room temperature to obtain the carbon nano onion.
The carbon nano-onions were subjected to TEM tests, and the test results were similar to example 1.
Example 3
According to the proportion of 110:1, polystyrene with the particle size of 40-60 nm and alumina ceramic balls with the diameter of 5mm are placed in a ball milling tank, and the ball milling tank is vacuumized to 1.0 multiplied by 10-3Pa, heating the ball milling tank to 200 ℃, carrying out ball milling (the rotating speed of the ball milling is 2000 r/min, the ball milling time is 3 hours), and cooling to room temperature to obtain the carbon nano onion。
The carbon nano-onions were subjected to TEM tests, and the test results were similar to example 1.
According to the embodiment, the carbon nano onion prepared by the preparation method provided by the invention is good in quality and high in purity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of carbon nano onion comprises the following steps:
under the vacuum condition, ball-milling a hydrocarbon polymer to obtain carbon nano onions;
the particle size of the hydrocarbon polymer is 10-100 nm.
2. The method according to claim 1, wherein the hydrocarbon polymer is one or more selected from polyethylene, polypropylene and polystyrene.
3. The method of claim 1, wherein the ball milling temperature is 150 to 250 ℃.
4. The preparation method of claim 1, wherein the rotation speed of the ball milling is 400-2000 rpm, and the time of the ball milling is 2-4 hours.
5. The preparation method of claim 1, wherein the ball-milling has a ball-to-material ratio of (80-120): 1.
6. the method of claim 1, wherein the milling balls for ball milling are ceramic balls;
the ceramic balls are aluminum oxide ceramic balls, zirconium oxide ceramic balls or silicon nitride ceramic balls.
7. The method according to claim 1 or 6, wherein the grinding balls for ball milling have a diameter of 3 to 12 mm.
8. The method of claim 1, wherein the vacuum is 1.0 x 10 or less-2Pa。
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| CN105271170B (en) * | 2015-11-03 | 2017-04-19 | 山西中兴环能科技有限公司 | Preparation method of nano carbon and composite material of nano carbon |
| CN108220908B (en) * | 2017-12-18 | 2019-11-05 | 中国科学院兰州化学物理研究所 | A kind of method that graphene and onion realization superslide is formed in situ in frictional interface |
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| CN109650380B (en) * | 2019-01-21 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Method for preparing carbon nano onion by dry friction in vacuum environment |
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