CN110255542A - A kind of grapheme tube and preparation method thereof - Google Patents
A kind of grapheme tube and preparation method thereof Download PDFInfo
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Abstract
A kind of grapheme tube of the invention and preparation method thereof, following quality proportioning component is prepared in grapheme tube, grade ball: powder material=(3-6): 1, powder material is in mass ratio (490-2000): 1 micro-sized metal powder and graphene.Preparation method are as follows: stock up on demand, graphene, micron order powder and grade ball are put into ball grinder and are mixed according to the ratio, and corresponding amount solvent is added into spheroidal graphite tank, after ball grinder is vacuumized, control Ball-milling Time and revolving speed carry out ball milling, after the completion, powder is dried, grapheme tube is made.The present invention is effectively improved graphene agglomeration traits using ethanol solution dispersion, the synergistic effect of sizes of balls is equipped with the milling atmosphere of semidry method, graphene can form grapheme tube, condition is controllable, it is easy to operate, cost is relatively low, can stablize under selected parameter and grapheme tube is made, and the grapheme tube of preparation has superperformance.
Description
Technical field:
The invention belongs to technical field of nano material, and in particular to a kind of grapheme tube and preparation method thereof.
Background technique:
Graphene is that carbon atom gathers the close honeycomb-like planar structure of the hexangle type rearranged, is only one carbon atom
The two-dimentional carbon nanomaterial of thickness.Grapheme tube is a kind of nanoscale structures made of being crimped as graphene.It can be used for compound
The neck such as material, energy storage, microprobe, micromechanical component, microelectronic component, microcircuit, military aerospace, armor facing and sensor
Domain.Nano materials research impetus temperature does not subtract in recent years, and graphene is concerned, and grapheme tube is even more to have a extensive future.
Mainly use chemical method in existing publication, chemical method by chemical agent concentration match etc. it is many-sided because
Element influences, and stability is poor.The method of the present invention belongs to physical method, and grapheme tube can be stably obtained under the parameter of optimization.
Summary of the invention:
The purpose of the present invention is overcoming above-mentioned the shortcomings of the prior art, a kind of grapheme tube and its preparation side are provided
Method, this method are based on semidry method ball milling and sizes of balls synergistic effect and grapheme tube are made in graphene.
To achieve the above object, the invention adopts the following technical scheme:
A kind of grapheme tube, including following quality proportioning component are prepared, in mass ratio, grade ball: powder material=(3-
6): 1, the powder material is micro-sized metal powder and graphene, in mass ratio, micron order powder: graphene=(490-2000): 1.
The grade bulb diameter is 2-5mm, and the grade ball material is stainless steel ball, zirconia ball or agate
Ball.
The micro-sized metal powder is one of cast aluminium powder, titanium valve or copper powder, the micro-sized metal Powder Particle Size
For 60-120 mesh.
The grapheme tube diameter is 30-50nm.
The conductivity of the grapheme tube is 300-1400S/cm, and carbon-to-oxygen ratio is (1-12): 1.
A kind of preparation method of grapheme tube, comprising the following steps:
Step 1, it stocks up:
(1) prepare micro-sized metal powder, the micro-sized metal Powder Particle Size is 60-120 mesh；
(2) prepare solvent, wherein the solvent is dehydrated alcohol or acetone；
(3) prepared by graphene:
Graphene is prepared using oxidizing process, plavini, CVD method or mechanical stripping method；
(4) prepare grade ball, grade bulb diameter is 2-5mm；
Step 2, prepared by grapheme tube:
(1) in mass ratio, grade ball: powder material=(3-6): 1, the powder material be micro-sized metal powder and graphene,
In mass ratio, micron order powder: graphene=(500-2000): 1, graphene, micron order powder and grade ball are put into ball grinder
In, mixture is formed, and solvent is added into spheroidal graphite tank, the proportion of mixture and solvent is 12:(1~2), unit g:ml,
After ball grinder is vacuumized, it is put into ball mill, ball milling 6h-12h, rotational speed of ball-mill 250-500r/min；
(2) after ball milling stops, powder is dried, grapheme tube is made.
In the step 1 (1), metal powder is one of cast aluminium powder, titanium valve or copper powder.
In the step 1 (3), the graphene of preparation is few layer graphene.
In the step 1 (3), oxidizing process prepares the detailed process of graphene are as follows:
Then plus deionization it is uniformly mixed with concentrated sulfuric acid 23ml, potassium permanganate 4g, graphite 1g, 30min is reacted at 40 DEG C,
Water dilution, adds 30% hydrogen peroxide of 5ml mass concentration to remove potassium permanganate, is washed with 10% dilute hydrochloric acid of mass concentration of 250ml, most
30 degrees Celsius of lower forced air dryings are being not higher than afterwards, are obtaining graphene.
In the step 1 (3), the specific preparation process of graphene of plavini preparation are as follows:
Intercalation expansible graphite raw material is taken, after 600-800 DEG C of Muffle furnace 1~4min of expansion, graphene is made.
In the step 1 (3), expanded graphite alkene raw material is that the 1395 model intercalation expansible graphites that the U.S. purchases are former
Material.
In the step 1 (4), the grade ball material is one in stainless steel ball, zirconia ball or agate ball
Kind.
In the step 2 (1), graphene is using preceding addition solvent, ultrasonic vibration 1h-2h, and purpose makes Multi-layer graphite
Alkene forms few layer graphene in a solvent, and the solvent is dehydrated alcohol.
In the step 2 (1), grade ball is using preceding addition solvent, and ultrasonic vibration 20min-40min is described
Solvent is dehydrated alcohol.
In the step 2 (1), it is 4.0 × 10 that spheroidal graphite tank, which is evacuated to vacuum degree,-2Pa。
In the step 2 (1), in mechanical milling process, every 30min stops 5-15min.
In the preparation process of grapheme tube of the invention, using micron order powder as main body, while grade ball work is added
For auxiliary, using the synergistic effect Graphite alkene of micron order powder and grade ball, grapheme tube can be made.Ball milling mistake simultaneously
The selection of ball milling solvent amount is also the key condition that grapheme tube is made in graphene in journey.
Beneficial effects of the present invention:
The present invention utilizes ethanol solution dispersed graphite alkene, to be effectively improved graphene agglomeration traits, the association of sizes of balls
The milling atmosphere graphene that same-action is equipped with semidry method can form grapheme tube, and condition is controllable, and easy to operate, cost is relatively low,
It can stablize under selected parameter and grapheme tube is made.
Detailed description of the invention:
Fig. 1 is the preparation method flow chart of steps of the grapheme tube of embodiment 1；
Fig. 2 is the SEM figure under 500 times of scanning electron microscope of grapheme tube prepared by embodiment 3；
Fig. 3 is the SEM figure under 2K times of scanning electron microscope of grapheme tube prepared by embodiment 3；
Fig. 4 is the SEM figure under 10K times of scanning electron microscope of grapheme tube prepared by embodiment 3；
Fig. 5 is the SEM figure under 20K times of scanning electron microscope of grapheme tube prepared by embodiment 3.
Fig. 6 is 40000 times of TEM figure that grapheme tube is made in embodiment 3；
Fig. 7 is the 5K times of SEM figure for the flake graphite alkene that comparative example 2 obtains；
Fig. 8 is the 20K times of SEM figure for the flake graphite alkene that comparative example 2 obtains；
Fig. 9 is the 50K times of SEM figure for the flake graphite alkene that comparative example 2 obtains.
Specific embodiment:
Below with reference to embodiment, the present invention is described in further detail.
In following embodiment:
Ultrasonic device the model KQ3200B, supersonic frequency 40KHZ of use；
Ball mill selects high-energy planetary ball mill machine；
Oxidizing process prepares the detailed process of graphene are as follows:
Then plus deionization it is uniformly mixed with concentrated sulfuric acid 23ml, potassium permanganate 4g, graphite 1g, 30min is reacted at 40 DEG C,
Water dilution, adds 30% hydrogen peroxide of 5ml mass concentration to remove potassium permanganate, is washed with 10% dilute hydrochloric acid of mass concentration of 250ml, most
30 degrees Celsius of lower forced air dryings are being not higher than afterwards, are obtaining graphene.
The specific preparation process of graphene of plavini preparation are as follows:
The 1395 model intercalation expansible graphite raw materials that the U.S. purchases are taken, by 600-800 DEG C of Muffle furnace 1~4min of expansion
Afterwards, graphene is made；
The graphene abbreviation graphene oxide of oxidizing process preparation, the graphene abbreviation expanded graphite alkene of plavini preparation；Oxygen
Graphite alkene yu expanded graphite alkene result formats are few layer of graphene；
Grade ball is added before ball grinder, after dehydrated alcohol progress ultrasonic vibration 20min is added, rinses and dries
It is dry, add ball grinder；
Graphene is before use, according to the ratio, graphene: dehydrated alcohol=1:300, unit g:ml are added to absolute ethanol
Ultrasonic vibration 1h adds ball grinder so that multi-layer graphene concussion is few layer graphene；
The grade ball used in Examples 1 to 3 and comparative example 1~3 is the stainless steel ball of diameter 3mm；
The grade ball used in embodiment 4~5 is the zirconia ball of diameter 2mm；
The grade ball used in embodiment 6 is the agate ball of diameter 2mm.
Embodiment 1
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (cast aluminium powder
ZL114A:+ expanded graphite alkene)=5:1, cast aluminium powder ZL114A: expanded graphite alkene=1999:1, by graphene, cast aluminium powder
ZL114A and grade ball are put into ball grinder, are formed mixture, and dehydrated alcohol are added into spheroidal graphite tank, mixture with it is anhydrous
The proportion of ethyl alcohol is 600:60, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put by Pa
Ball mill, ball milling duration 8h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, graphite is made
Alkene pipe, diameter 42-45nm, conductivity 1000-1200S/cm, carbon-to-oxygen ratio 10:1.
Embodiment 2
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (titanium alloy
TC4 powder+expanded graphite alkene)=4:1, titanium alloy TC 4 powder: expanded graphite alkene=1999:1, by graphene, titanium alloy TC 4
Powder and grade ball are put into ball grinder, form mixture, and dehydrated alcohol is added into spheroidal graphite tank, mixture and anhydrous second
The proportion of alcohol is 600:60, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put into ball by Pa
Grinding machine, ball milling duration 8h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, graphene is made
Pipe, diameter 46-48nm, conductivity 1000-1200S/cm, carbon-to-oxygen ratio 10:1.
Embodiment 3
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (cast aluminium powder
ZL114A+ expanded graphite alkene)=5:1, cast aluminium powder ZL114A: expanded graphite alkene=499:1, by graphene, cast aluminium powder ZL114A
It is put into ball grinder with grade ball, forms mixture, and dehydrated alcohol is added into spheroidal graphite tank, mixture and dehydrated alcohol
Proportion is 600:60, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put into ball mill by Pa,
Ball milling duration 8h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, grapheme tube is made, directly
Diameter is 30-34nm, conductivity 1360-1400S/cm, carbon-to-oxygen ratio 12:1.SEM under 500 times of scanning electron microscope of the grapheme tube
Figure as shown in Fig. 2, under 2K times of scanning electron microscope SEM figure as shown in figure 3, under 10K times of scanning electron microscope SEM figure as shown in figure 4,
SEM figure under 20K times of scanning electron microscope is as shown in figure 5, the TEM figure under 40000 times of transmission electron microscopes is as shown in Figure 6.
Comparative example 1: applicant it has been investigated that: grade ball and graphene ball milling, which is used alone, can not be made graphene
Pipe, micron order powder and graphene ball milling, which is used alone, can not be made grapheme tube.It tests as follows: being put into grade in ball grinder
Ball and expanded graphite alkene, under 3 same experimental conditions of the present embodiment, sheet non-tubular shape is finally still presented in expanded graphite alkene.
Micron order powder and expanded graphite alkene are simply placed in ball grinder, under 3 same experimental conditions of embodiment, expanded graphite alkene finally according to
Old presentation sheet non-tubular shape.
Embodiment 4
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (cast aluminium powder
ZL114A+ graphene oxide)=5:1, cast aluminium powder ZL114A: graphene oxide=1999:1, by graphene, cast aluminium powder ZL114A
It is put into ball grinder with grade ball, forms mixture, and dehydrated alcohol is added into spheroidal graphite tank, mixture and dehydrated alcohol
Proportion is 600:80, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put into ball mill by Pa,
Ball milling duration 10h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, grapheme tube is made, directly
Diameter is 38-40nm, and conductivity 900-1050S/cm, carbon-to-oxygen ratio is (8-10): 1.
Embodiment 5
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (cast aluminium powder
ZL114A+ graphene oxide)=5:1, cast aluminium powder ZL114A: graphene oxide=499:1, by graphene, cast aluminium powder ZL114A
It is put into ball grinder with grade ball, forms mixture, and dehydrated alcohol is added into spheroidal graphite tank, mixture and dehydrated alcohol
Proportion is 600:80, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put into ball mill by Pa,
Ball milling duration 8h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, grapheme tube is made, directly
Diameter is 39-42nm, and conductivity 800-1000S/cm, carbon-to-oxygen ratio is (6-9): 1.
Embodiment 6
A kind of preparation method of grapheme tube, flow chart of steps is as shown in Figure 1, in mass ratio, grade ball: (titanium alloy
TC4 powder+graphene oxide)=5:1, titanium alloy TC 4 powder: graphene oxide=1999:1, by graphene, titanium alloy TC 4
Powder and grade ball are put into ball grinder, form mixture, and dehydrated alcohol is added into spheroidal graphite tank, mixture and anhydrous second
The proportion of alcohol is 600:80, unit g:ml.Ball grinder is vacuumized, vacuum degree is 4.0 × 10-2Ball grinder is put into ball by Pa
Grinding machine, ball milling duration 10h (every 30min stops 15min), adjusts rotational speed of ball-mill 250r/min, dries after ball milling, graphene is made
Pipe, diameter 40-50nm, conductivity 300-600S/cm, carbon-to-oxygen ratio are (1-4): 1.
Comparative example 2
Wet ball grinding, in mass ratio, grade ball: (cast aluminium powder ZL114A+ expanded graphite alkene)=5:1, cast aluminium powder
ZL114A: graphene, cast aluminium powder ZL114A and grade ball are put into ball grinder by expanded graphite alkene=499:1, form mixing
Object, and dehydrated alcohol is added into spheroidal graphite tank, the proportion of mixture and dehydrated alcohol is 600:160, unit g:ml.By ball milling
Tank vacuumizes, and vacuum degree is 4.0 × 10-2Ball grinder is put into ball mill by Pa, ball milling duration 12h (every 30min stops 15min),
Rotational speed of ball-mill 250r/min is adjusted, is dried after ball milling, graphene obtained is still sheet, the SEM figure under 5K times of scanning electron microscope
As shown in fig. 7, the SEM figure under 20K times of scanning electron microscope is as shown in figure 8, the SEM figure under 50K times of scanning electron microscope is as shown in Figure 9.
Comparative example 3
Dry ball milling, in mass ratio, grade ball: (cast aluminium powder ZL114A+)=5:1, cast aluminium powder ZL114A: expanded graphite
Graphene, cast aluminium powder ZL114A and grade ball are put into ball grinder by alkene=499:1, form mixture, ball grinder are taken out true
Sky, vacuum degree are 4.0 × 10-2Ball grinder is put into ball mill by Pa, and ball milling duration 12h (every 30min stops 15min) adjusts ball
Revolving speed 250r/min is ground, is dried after ball milling, graphene is reunited obviously, Cheng Tuanzhuan.
Claims (10)
1. a kind of grapheme tube, which is characterized in that it is prepared including following quality proportioning component, in mass ratio, grade ball:
Powder material=(3-6): 1, the powder material is micro-sized metal powder and graphene, in mass ratio, micron order powder: graphene=
(490-2000):1。
2. grapheme tube according to claim 1, which is characterized in that the grade bulb diameter is 2-5mm, described
Grade ball material is stainless steel ball, zirconia ball or agate ball.
3. grapheme tube according to claim 1, which is characterized in that the micro-sized metal powder is cast aluminium powder, titanium valve
Or one of copper powder, the micro-sized metal Powder Particle Size are 60-120 mesh.
4. grapheme tube according to claim 1, which is characterized in that the grapheme tube diameter is 30-50nm.
5. grapheme tube according to claim 1, which is characterized in that the conductivity of the grapheme tube is 300-
1400S/cm, carbon-to-oxygen ratio are (1-12): 1.
6. the preparation method of grapheme tube described in claim 1, which comprises the following steps:
Step 1, it stocks up:
(1) prepare micro-sized metal powder, the micro-sized metal Powder Particle Size is 60-120 mesh；
(2) prepare solvent, wherein the solvent is dehydrated alcohol or acetone；
(3) prepared by graphene:
Graphene is prepared using oxidizing process, plavini, CVD method or mechanical stripping method；
(4) prepare grade ball, grade bulb diameter is 2-5mm；
Step 2, prepared by grapheme tube:
(1) in mass ratio, grade ball: powder material=(3-6): 1, the powder material is micro-sized metal powder and graphene, by matter
Ratio is measured, micron order powder: graphene=(500-2000): 1, graphene, micron order powder and grade ball are put into ball grinder, shape
Resulting mixture, and solvent is added into spheroidal graphite tank, the proportion of mixture and solvent is 12:(1~2), unit g:ml, by ball milling
After tank vacuumizes, it is put into ball mill, ball milling 6h-12h, rotational speed of ball-mill 250-500r/min；
(2) after ball milling stops, powder is dried, grapheme tube is made.
7. the preparation method of grapheme tube according to claim 6, which is characterized in that in the step 2 (1), graphite
Alkene is using preceding addition solvent, ultrasonic vibration 1h-2h, and the solvent is dehydrated alcohol.
8. the preparation method of grapheme tube according to claim 6, which is characterized in that in the step 2 (1), millimeter
Grade ball is using preceding addition solvent, ultrasonic vibration 20min-40min, and the solvent is dehydrated alcohol.
9. the preparation method of grapheme tube according to claim 6, which is characterized in that in the step 2 (1), spheroidal graphite
It is 4.0 × 10 that tank, which is evacuated to vacuum degree,-2Pa。
10. the preparation method of grapheme tube according to claim 6, which is characterized in that in the step 2 (1), ball milling
In the process, every 30min stops 5-15min.
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| CN113617377A (en) * | 2021-09-03 | 2021-11-09 | 沈阳航空航天大学 | Vanadium-doped carbon nitride photocatalyst, and preparation method and application thereof |
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