CN110255542B - Graphene tube and preparation method thereof - Google Patents

Graphene tube and preparation method thereof Download PDF

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CN110255542B
CN110255542B CN201910572757.0A CN201910572757A CN110255542B CN 110255542 B CN110255542 B CN 110255542B CN 201910572757 A CN201910572757 A CN 201910572757A CN 110255542 B CN110255542 B CN 110255542B
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graphene
ball milling
powder
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preparing
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CN110255542A (en
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杨光
孟庆实
李鹏旭
王天琦
张硕程
任宇航
王维
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Shenyang Aerospace University
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

According to the graphene tube and the preparation method thereof, the graphene tube is prepared from the following components in parts by mass: powder material (3-6): 1, the powder material is micron-sized metal powder and graphene according to the mass ratio (490) -2000) of 1. The preparation method comprises the following steps: preparing materials as required, putting graphene, micron-sized powder and millimeter-sized balls into a ball milling tank according to a ratio, mixing, adding a corresponding amount of solvent into the ball milling tank, vacuumizing the ball milling tank, controlling ball milling time and rotating speed to perform ball milling, and drying powder to obtain the graphene tube after finishing ball milling. According to the invention, the problem of graphene agglomeration is effectively improved by using the dispersion of an absolute ethyl alcohol solution, the graphene tube can be formed by graphene under the synergistic effect of the large balls and the ball milling environment of a semi-dry method, the conditions are controllable, the operation is simple, the cost is low, the graphene tube can be stably prepared under the selected parameters, and the prepared graphene tube has good performance.

Description

Graphene tube and preparation method thereof
The technical field is as follows:
the invention belongs to the technical field of nano materials, and particularly relates to a graphene tube and a preparation method thereof.
Background art:
graphene is a hexagonal honeycomb-shaped planar structure formed by densely arranging carbon atoms, and is a two-dimensional carbon nano material with the thickness of only one carbon atom. The graphene tube is a nanoscale structure formed by curling graphene. It can be used in the fields of composite materials, energy storage, microprobe, micro mechanical element, microelectronic device, microcircuit, military and aerospace, armor protection and sensor, etc. In recent years, the research momentum of nano materials is not reduced, the attention of graphene is paid, and the graphene tube has a wide prospect.
The existing patent mainly adopts a chemical method, and the chemical method is influenced by various factors such as concentration ratio of chemical reagents and the like, so that the stability is poor. The method belongs to a physical method, and the graphene tube can be stably obtained under optimized parameters.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides a graphene tube and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the graphene tube is prepared from the following components in parts by mass: powder material (3-6): 1, the powder is micron-sized metal powder and graphene, and the micron-sized metal powder comprises the following components in percentage by mass: and (490) -2000 is 1.
The diameter of the millimeter-scale ball is 2-5mm, and the millimeter-scale ball is made of stainless steel balls, zirconia balls or agate balls.
The micron-sized metal powder is one of cast aluminum powder, titanium powder or copper powder, and the particle size of the micron-sized metal powder is 60-120 meshes.
The diameter of the graphene tube is 30-50 nm.
The conductivity of the graphene tube is 300-1400S/cm, and the carbon-oxygen ratio is (1-12): 1.
a preparation method of a graphene tube comprises the following steps:
step 1, preparing materials:
(1) preparing micron-sized metal powder, wherein the granularity of the micron-sized metal powder is 60-120 meshes;
(2) preparing a solvent, wherein the solvent is absolute ethyl alcohol or acetone;
(3) preparing graphene:
preparing graphene by adopting an oxidation method, an expansion method, a CVD method or a mechanical stripping method;
(4) preparing millimeter-scale balls with the diameter of 2-5 mm;
step 2, preparing a graphene tube:
(1) according to the mass ratio, millimeter-sized balls: powder material (3-6): 1, the powder is micron-sized metal powder and graphene, and the micron-sized metal powder comprises the following components in percentage by mass: and (500) -2000) placing the graphene, the micron-grade powder and the millimeter-grade ball into a ball milling tank to form a mixture, and adding a solvent into the ball milling tank, wherein the ratio of the mixture to the solvent is 12: (1-2), wherein the unit is g: ml, the ball milling tank is vacuumized and then placed into a ball mill for ball milling for 6-12 h, and the ball milling rotating speed is 250-500 r/min;
(2) and after the ball milling is stopped, drying the powder to obtain the graphene tube.
In the step 1(1), the metal powder is one of cast aluminum powder, titanium powder or copper powder.
In the step 1(3), the prepared graphene is few-layer graphene.
In the step 1(3), the specific process of preparing graphene by the oxidation method comprises:
uniformly mixing 23ml of concentrated sulfuric acid, 4g of potassium permanganate and 1g of graphite, reacting at 40 ℃ for 30min, diluting with deionized water, adding 5ml of 30% hydrogen peroxide to remove the potassium permanganate, washing with 250ml of 10% diluted hydrochloric acid, and finally drying by blowing at the temperature of not higher than 30 ℃ to obtain the graphene.
In the step 1(3), the specific preparation process of the graphene prepared by the expansion method is as follows:
taking the intercalation expandable graphite raw material, and expanding for 1-4 min at the temperature of 800 ℃ through a muffle furnace to obtain the graphene.
In the step 1(3), the expanded graphene raw material is 1395 model intercalated expandable graphite raw material purchased from the United states.
In the step 1 and the step 4, the millimeter-scale balls are made of one of stainless steel balls, zirconia balls and agate balls.
In the step 2(1), a solvent is added into the graphene before use, and the graphene is subjected to ultrasonic oscillation for 1h-2h, so that the few-layer graphene is formed by the multilayer graphene in the solvent, wherein the solvent is absolute ethyl alcohol.
In the step 2(1), a solvent is added into the millimeter-sized ball before use, and the ultrasonic vibration is carried out for 20min to 40min, wherein the solvent is absolute ethyl alcohol.
In the step 2(1), the spherical ink tank is vacuumized until the vacuum degree is 4.0 multiplied by 10 -2 Pa。
In the step 2(1), stopping for 5-15min every 30min in the ball milling process.
In the preparation process of the graphene tube, micron-sized powder is used as a main body, the millimeter-sized balls are added as an auxiliary, and the graphene is ball-milled by utilizing the synergistic effect of the micron-sized powder and the millimeter-sized balls, so that the graphene tube can be prepared. Meanwhile, the selection of the amount of the ball milling solvent in the ball milling process is also a key condition for preparing the graphene tube from the graphene.
The invention has the beneficial effects that:
according to the invention, the graphene is dispersed by using the absolute ethyl alcohol solution, so that the problem of graphene agglomeration is effectively improved, the graphene tube can be formed by matching the synergistic effect of the large balls and the graphene in the ball milling environment of the semi-dry method, the conditions are controllable, the operation is simple, the cost is lower, and the graphene tube can be stably manufactured under the selected parameters.
Description of the drawings:
fig. 1 is a flow chart of the steps of a method of making the graphene tube of example 1;
FIG. 2 is an SEM image of a graphene tube prepared in example 3 under a scanning electron microscope of 500 times;
FIG. 3 is an SEM image of the graphene tube prepared in example 3 under a 2K-fold scanning electron microscope;
FIG. 4 is an SEM image of a graphene tube prepared in example 3 under a scanning electron microscope of 10K times;
fig. 5 is an SEM image of the graphene tube prepared in example 3 under a scanning electron microscope of 20K times.
FIG. 6 is a 40000-fold TEM image of a graphene tube prepared in example 3;
fig. 7 is a 5K-fold SEM image of the graphene platelets obtained in comparative example 2;
fig. 8 is a 20K-fold SEM image of the graphene platelets obtained in comparative example 2;
fig. 9 is a 50K-fold SEM image of the graphene platelets obtained in comparative example 2.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples.
In the following examples:
the model of the adopted ultrasonic equipment is KQ3200B, and the ultrasonic frequency is 40 KHZ;
the ball mill adopts a high-energy planetary ball mill;
the specific process for preparing the graphene by the oxidation method comprises the following steps:
uniformly mixing 23ml of concentrated sulfuric acid, 4g of potassium permanganate and 1g of graphite, reacting at 40 ℃ for 30min, diluting with deionized water, adding 5ml of 30% hydrogen peroxide with mass concentration to remove the potassium permanganate, washing with 250ml of 10% dilute hydrochloric acid with mass concentration, and finally drying by blowing at the temperature of not higher than 30 ℃ to obtain the graphene.
The specific preparation process of the graphene prepared by the expansion method comprises the following steps:
taking a 1395 type intercalated expandable graphite raw material purchased in America, and expanding the raw material for 1-4 min at 800 ℃ through a muffle furnace to prepare graphene;
graphene prepared by an oxidation method is abbreviated as graphene oxide, and graphene prepared by an expansion method is abbreviated as expanded graphene; the result forms of the graphene oxide yu expanded graphene are all few-layer graphene;
adding the millimeter-sized balls into a ball milling tank, adding absolute ethyl alcohol, performing ultrasonic oscillation for 20min, washing, drying, and adding into the ball milling tank;
before the graphene is used, the graphene is prepared from the following components in percentage by weight: absolute ethanol-1: 300, unit g: adding the mixture into absolute ethyl alcohol, performing ultrasonic oscillation for 1 hour to enable multilayer graphene to oscillate into few-layer graphene, and adding the few-layer graphene into a ball-milling tank;
the millimeter-sized balls used in examples 1 to 3 and comparative examples 1 to 3 were stainless steel balls having a diameter of 3 mm;
the millimeter-sized balls adopted in the embodiments 4 to 5 are zirconia balls with the diameter of 2 mm;
the millimeter-sized balls used in example 6 were agate balls having a diameter of 2 mm.
Example 1
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (cast aluminum powder ZL 114A: + expanded graphene) ═ 5: 1, cast aluminum powder ZL 114A: 1, placing graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 60 in g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 Pa, placing the ball milling tank into a ball mill, performing ball milling for 8 hours (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, and drying after ball milling to obtain the graphene tube with the diameter42-45nm, the conductivity is 1000-1200S/cm, and the carbon-oxygen ratio is 10: 1.
Example 2
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (titanium alloy TC4 powder + expanded graphene) 4: 1, titanium alloy TC4 powder: 1, placing graphene, titanium alloy TC4 powder and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 60 in g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 Pa, putting the ball milling tank into a ball mill, adjusting the ball milling rotation speed to 250r/min, and drying after ball milling for 8h (stopping for 15min every 30 min) to prepare the graphene tube with the diameter of 46-48nm, the conductivity of 1000-1200S/cm and the carbon-oxygen ratio of 10: 1.
Example 3
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (cast aluminum powder ZL114A + expanded graphene) 5: 1, cast aluminum powder ZL 114A: 499:1, putting the graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 60, unit is g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 And Pa, putting the ball milling tank into a ball mill, performing ball milling for 8 hours (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, and drying after ball milling to obtain the graphene tube with the diameter of 30-34nm, the conductivity of 1360 and 1400S/cm and the carbon-oxygen ratio of 12: 1. An SEM image of the graphene tube under a 500-fold scanning electron microscope is shown in FIG. 2, an SEM image under a 2K-fold scanning electron microscope is shown in FIG. 3, an SEM image under a 10K-fold scanning electron microscope is shown in FIG. 4, an SEM image under a 20K-fold scanning electron microscope is shown in FIG. 5, and a TEM image under a 40000-fold transmission electron microscope is shown in FIG. 6.
Comparative example 1: the applicant finds out through research that: graphene tubes cannot be prepared by using millimeter-sized balls and graphene ball milling alone, and graphene tubes cannot be prepared by using micron-sized powder and graphene ball milling alone. The experiments were as follows: millimeter-sized balls and expanded graphene are placed in a ball milling tank, and under the same experimental conditions of this example 3, the expanded graphene still finally appears in a lamellar non-tubular shape. Only micron-sized powder and expanded graphene are put into the ball milling tank, and under the same experimental conditions of example 3, the expanded graphene still finally presents a lamellar non-tubular shape.
Example 4
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (cast aluminum powder ZL114A + graphene oxide) ═ 5: 1, cast aluminum powder ZL 114A: 1, putting graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 80 in g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 And Pa, putting the ball milling tank into a ball mill, ball milling for 10 hours (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, and drying after ball milling to obtain the graphene tube with the diameter of 38-40nm, the conductivity of 900 plus 1050S/cm and the carbon-oxygen ratio of (8-10): 1.
Example 5
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (cast aluminum powder ZL114A + graphene oxide) ═ 5: 1, cast aluminum powder ZL 114A: putting graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 80 in g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 And Pa, putting the ball milling tank into a ball mill, wherein the ball milling time is 8 hours (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, and drying after ball milling to obtain the graphene tube with the diameter of 39-42nm, the conductivity of 800-1000S/cm and the carbon-oxygen ratio of (6-9): 1.
Example 6
A preparation method of a graphene tube comprises the following steps of as shown in figure 1, by mass ratio: (titanium alloy TC4 powder + graphene oxide) ═ 5: 1, titanium alloy TC4 powder: 1999:1, putting graphene, titanium alloy TC4 powder and millimeter-sized balls into a ball milling tank to form a mixture, and adding graphene oxide into the ball milling tankThe mixture ratio of the mixture to the absolute ethyl alcohol is 600: 80 in g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 Pa, placing the ball milling tank into a ball mill, wherein the ball milling time is 10h (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, and drying after ball milling to prepare the graphene tube, wherein the diameter is 40-50nm, the conductivity is 300-600S/cm, and the carbon-oxygen ratio is (1-4): 1.
comparative example 2
Wet ball milling, according to the mass ratio, millimeter level ball: (cast aluminum powder ZL114A + expanded graphene) 5: 1, cast aluminum powder ZL 114A: 499:1, putting the graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, and adding absolute ethyl alcohol into the ball milling tank, wherein the ratio of the mixture to the absolute ethyl alcohol is 600: 160, unit is g: ml. The ball milling tank is vacuumized, and the vacuum degree is 4.0 multiplied by 10 -2 Pa, putting the ball milling tank into a ball mill, performing ball milling for 12h (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, performing ball milling, and drying to obtain the graphene which is still lamellar, wherein an SEM image under a scanning electron microscope of 5K times is shown in fig. 7, an SEM image under a scanning electron microscope of 20K times is shown in fig. 8, and an SEM image under a scanning electron microscope of 50K times is shown in fig. 9.
Comparative example 3
Dry ball milling, namely, according to the mass ratio, a millimeter-sized ball: (cast aluminum powder ZL114A +) -5: 1, cast aluminum powder ZL 114A: 499 a: 1 expanded graphene, placing the graphene, cast aluminum powder ZL114A and millimeter-sized balls into a ball milling tank to form a mixture, vacuumizing the ball milling tank, and ensuring that the vacuum degree is 4.0 multiplied by 10 -2 And Pa, putting the ball milling tank into a ball mill, carrying out ball milling for 12h (stopping for 15min every 30 min), adjusting the ball milling rotation speed to 250r/min, drying after ball milling, and obviously agglomerating the graphene to form agglomerates.

Claims (8)

1. The preparation method of the graphene tube is characterized in that the graphene tube is prepared from the following components in parts by mass: powder = (3-6): 1, the powder materials are micron-sized metal powder and graphene, the micron-sized metal powder is one of cast aluminum powder, titanium powder or copper powder, and the micron-sized metal powder comprises the following components in percentage by mass: graphene = (490) -2000: 1;
the method comprises the following steps:
step 1, preparing materials:
(1) preparing micron-sized metal powder, wherein the granularity of the micron-sized metal powder is 60-120 meshes;
(2) preparing a solvent, wherein the solvent is absolute ethyl alcohol or acetone;
(3) preparing graphene:
preparing graphene by adopting an oxidation method, an expansion method, a CVD method or a mechanical stripping method;
(4) preparing millimeter-scale balls with the diameter of 2-5 mm;
step 2, preparing a graphene tube:
(1) according to the mass ratio, millimeter-sized balls: powder = (3-6): 1, the powder is micron-sized metal powder and graphene, and the micron-sized metal powder comprises the following components in percentage by mass: and 1, placing the graphene, micron-sized powder and millimeter-sized balls into a ball milling tank to form a mixture, and adding a solvent into the ball milling tank, wherein the ratio of the mixture to the solvent is 12: (1-2), wherein the unit is g: ml, the ball milling tank is vacuumized and then placed into a ball mill for ball milling for 6-12 h, and the ball milling rotating speed is 250-500 r/min;
(2) and after the ball milling is stopped, drying the powder to prepare the graphene tube, wherein the conductivity of the graphene tube is 800-1400S/cm, and the carbon-oxygen ratio is (6-12): 1.
2. the preparation method of the graphene tube according to claim 1, wherein the diameter of the millimeter-sized ball is 2-5mm, and the millimeter-sized ball is made of stainless steel balls, zirconia balls or agate balls.
3. The method according to claim 1, wherein the micron-sized metal powder has a particle size of 60-120 mesh.
4. The method for preparing the graphene tube according to claim 1, wherein the diameter of the graphene tube is 30-50 nm.
5. The method for preparing the graphene tube according to claim 1, wherein in the step 2(1), a solvent is added to the graphene before use, and the graphene is subjected to ultrasonic oscillation for 1h-2h, wherein the solvent is absolute ethyl alcohol.
6. The method for preparing the graphene tube according to claim 1, wherein in the step 2(1), a solvent is added into the millimeter-sized spheres before use, and the solvent is absolute ethyl alcohol and is subjected to ultrasonic oscillation for 20min to 40 min.
7. The method for preparing graphene tubes according to claim 1, wherein in step 2(1), the spherical ink tanks are evacuated to a vacuum degree of 4.0 x 10 -2 Pa。
8. The method for preparing the graphene tube according to claim 1, wherein in the step 2(1), the ball milling process is stopped for 5-15min every 30 min.
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