CN110923591A - Preparation method and application of graphene - Google Patents
Preparation method and application of graphene Download PDFInfo
- Publication number
- CN110923591A CN110923591A CN201911034547.2A CN201911034547A CN110923591A CN 110923591 A CN110923591 A CN 110923591A CN 201911034547 A CN201911034547 A CN 201911034547A CN 110923591 A CN110923591 A CN 110923591A
- Authority
- CN
- China
- Prior art keywords
- rolling
- pure copper
- graphite paper
- graphene
- copper sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/20—Making alloys containing metallic or non-metallic fibres or filaments by subjecting to pressure and heat an assembly comprising at least one metal layer or sheet and one layer of fibres or filaments
-
- 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
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of graphene, wherein graphite paper with (002) texture is clamped between pure copper sheets, and continuous multi-pass accumulated rolling is carried out on the graphite paper under the condition of no lubrication at room temperature. The graphite paper has a specific texture, namely, the inner layers of the graphite paper are parallel to each other and are all parallel to the rolling direction, under the action of the rolling force, the pure copper sheets are subjected to severe plastic deformation to enable the layers of the graphite paper to be subjected to shear stress parallel to the rolling direction, the shear stress is greater than van der Waals force between the inner layers of the graphite paper, the layers of the graphite paper begin to be stripped along the direction parallel to the rolling direction, the graphite paper is thinned layer by layer along with the increase of rolling passes, and finally the graphene is thinned into few-layer graphene. The equipment required by the method is an industrial rolling mill and a muffle furnace, the operation is simple, the cost is low, no pollution is caused, and the single-layer graphene can be prepared. The graphene/copper composite material with excellent strong plasticity, high strength and high conductivity can be obtained by carrying out hot rolling on the graphene and the pure copper sheet prepared by the method only once.
Description
Technical Field
The invention relates to a preparation method of graphene and a preparation method of an in-situ graphene reinforced copper-based composite material, belonging to the field of material preparation.
Background
Graphene is a polymer made of carbon atoms in sp2The hybridization is a combination mode to form a hexagonal honeycomb-shaped orderly-arranged two-dimensional material. Since the single-layer graphene was successfully prepared in 2004, the excellent properties of graphene have attracted extensive attention of researchers and industries. Graphene has a series of excellent properties: the strength of the material is as high as 130GPa, the material with the highest strength is known at present, and the theoretical specific surface area of the material is as high as 2630m2Per g, room temperature download flow mobility of about 15000cm2V.s, thermal conductivity as high as 5300W/mK, as low as 10-6Resistivity of Ω · cm. Due to the unique properties, the graphene has extremely high application value and potential in a plurality of fields such as composite materials, photoelectric devices and energy storage. At present, the preparation method of graphene mainly comprises the following steps: redox, epitaxial growth, chemical vapor deposition, and mechanical lift-off. The redox method is simple to operate and high in yield, but the graphene is low in quality, and meanwhile, strong acids such as sulfuric acid and nitric acid are used, so that a large amount of waste water is generated, and the environmental protection is not facilitated; the epitaxial growth method and the chemical vapor deposition method can prepare high-quality graphene, but the cost is high and the process is complex. Graphene prepared by a mechanical stripping method (such as a ball milling method) is low in quality, many in defects and low in efficiency, and industrial production cannot be realized. Therefore, the current preparation method is high in cost and has certain pollution property, and the high-quality graphene is required to meet industrial application.
The good electrical and thermal conductivity enables the pure copper to be widely applied in the electronic industry, but the application of the pure copper is greatly limited due to the low strength and hardness of the pure copper. In industry, the strength and hardness of pure copper are usually increased by alloying or adding ceramic particles, but the method significantly reduces the electrical and thermal conductivity of pure copper. Graphene is widely used in copper-based composite materials due to its good high strength and high conductivity, but other current research results show that: due to the addition of the graphene, on one hand, if good electric and thermal conductivity needs to be maintained, the strength of the composite material is not obviously improved; on the other hand, if the strength is greatly improved, the conductivity and plasticity are remarkably reduced. Possible reasons are: firstly, the number of graphene layers is less than 10, so that excellent high-strength and high-conductivity performance can be realized, the number of graphene layers in an original supply state is more than 10, and the number of graphene layers cannot be effectively reduced by a preparation process, namely the function of graphene cannot be fully exerted; secondly, the graphene has a high specific surface area and is easy to agglomerate, and the preparation process cannot effectively reduce the agglomeration of the graphene, namely the preparation process cannot realize a good dispersion effect of the graphene in a metal matrix; thirdly, the preparation process cannot enhance the bonding property of the graphene and the matrix.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a preparation method of graphene, which has the advantages of simple process, no pollution, low cost and high efficiency, can obtain high-quality graphene with low layer number, and simultaneously provides a preparation method of an in-situ graphene reinforced copper-based composite material.
The technical scheme provided by the invention is as follows:
the invention provides a preparation method of graphene, which comprises the following steps:
(1) annealing the pure copper sheet, and performing surface treatment on the annealed pure copper sheet to remove impurities on the surface of the pure copper sheet for later use;
(2) placing graphite paper with thickness less than or equal to 0.5mm and (002) texture between two pure copper sheets at room temperature, and starting rolling after the pure copper sheets clamp the graphite paper;
(3) after rolling for 5-30 times, taking out the pure copper sheets and the graphite paper therein, cutting the pure copper sheets and the graphite paper into small samples, placing the small samples between two pure copper sheets, and continuing rolling;
(4) and (4) repeating the step (3) until the cumulative rolling pass of the graphite paper is more than 100 times, thus obtaining the graphene with the number of layers less than or equal to 4.
The method comprises the following steps of pretreating the pure copper sheet before use, wherein the pretreatment mode is as follows: and (3) placing the pure copper sheet in a 500-700 ℃ tube furnace filled with argon protective gas for more than 2 hours, annealing, and carrying out surface treatment on the annealed pure copper sheet to remove an oxide film and grease on the surface.
The graphite paper is pretreated before use in the following way: the graphite paper is washed with acetone and deionized water several times and then dried at a temperature below 60 ℃.
The deformation amount of the control sample in the thickness direction per rolling is 50% or more.
Further:
and controlling the accumulated rolling pass to be more than or equal to 200 to obtain the graphene product with the layer number of 2.
And controlling the accumulated rolling pass to be more than or equal to 300 to obtain the graphene product with the layer number of 1.
The machine used for rolling is an industrial rolling mill, and the rolling speed is 100-300 mm/min.
The invention also provides a preparation method of the in-situ graphene reinforced copper-based composite material, which comprises the following steps:
(1) annealing the pure copper sheet, and performing surface treatment on the annealed pure copper sheet to remove impurities on the surface of the pure copper sheet for later use;
(2) placing graphite paper with the thickness less than or equal to 0.5mm between two pure copper sheets at room temperature, and starting rolling after the pure copper sheets clamp the graphite paper;
(3) after rolling for 5-30 times, taking out the pure copper sheets and the graphite paper therein, cutting the pure copper sheets and the graphite paper into small samples, placing the small samples between two pure copper sheets, and continuing rolling;
(4) repeating the step (3) until the cumulative rolling pass of the graphite paper is more than 100 times;
(5) and (4) placing the sample obtained in the step (4) into a muffle furnace at 500-700 ℃ for heat preservation, and then carrying out hot rolling for one pass.
Preferably: the hot rolling temperature is 600 ℃, and the heat preservation time is 10min
The strength of the graphene/copper composite material prepared by the method can reach up to 682MPa, the ductility can reach 14.4%, and the conductivity can reach up to 83% IACS, so that the composite material has good strong plasticity and conductivity.
The principle of the invention is as follows:
the method comprises the steps of clamping graphite paper between pure copper sheets subjected to complete annealing and surface treatment, and carrying out continuous multiple-accumulation pack rolling on the pure copper sheets under the condition of no lubrication at room temperature to prepare few-layer graphene. In order to ensure the effective thinning of the graphite under the rolling force, the raw material of the graphite paper used by the invention has a specific texture, specifically a (002) texture (as shown in figure 1); in the rolling process, the crystal face of graphite (002) is parallel to the rolling direction, namely, all the layers in the graphite paper are not only parallel to each other, but also parallel to the rolling direction, so that the special structure of the graphite paper can ensure that all the layers in the graphite paper are efficiently stripped along the rolling direction. In the rolling process, under the effect of rolling force, the pure copper sheet is subjected to plastic deformation, and then stress is uniformly transmitted to the graphite, so that the shearing stress parallel to the rolling direction is applied between the inner layers of the graphite, the shearing stress is greater than the van der Waals force between the inner layers of the graphite, the inner layers of the graphite begin to be stripped along the direction parallel to the rolling direction, and the graphite is thinned layer by layer along with the increase of rolling passes. The method adopts a method of adding the new copper sheet in a complete annealing state when the rolling is carried out to a certain pass, so that the copper sheet is always kept complete in the rolling process, namely the graphite paper is always subjected to the shearing force parallel to the rolling direction, and finally thinned into few-layer or even single-layer high-quality graphene. Finally, the prepared graphene with high quality and low layer number and a pure copper medium are subjected to hot rolling only once to obtain the graphene/copper composite material with excellent strong plasticity and high conductivity.
The invention uses acetone and deionized water to wash the graphite paper for a plurality of times to remove impurities on the surface of the graphite paper, and dries the graphite paper at low temperature. The invention carries out annealing treatment on the pure copper sheet, and aims to reduce the hardness of the pure copper sheet and improve the cutting processability of the pure copper sheet; the residual stress of the pure copper sheet is eliminated, the size is stabilized, and the deformation and crack tendency is reduced; refining crystal grains, adjusting the structure and eliminating the structure defects; the invention carries out surface treatment such as oxide film removal, degreasing and the like on the pure copper sheet in a complete annealing state so as to prevent the sample from being polluted.
Compared with the prior art, the invention has the beneficial effects that:
1. the graphene preparation method provided by the invention does not need to add a dispersing agent, is simple in process and has no chemical pollution.
2. The graphene preparation method provided by the invention can be used for preparing a graphene product with the number of layers being less than or equal to 4, the product quality is high, and the performance of the graphene can be fully shown.
3. The graphene preparation method provided by the invention has the advantages that the raw material is graphite paper, the equipment is an industrial rolling mill, and the cost is low.
4. The graphene preparation method provided by the invention uses an industrial rolling mill, is high in efficiency and is suitable for industrial production.
5. The preparation method of the in-situ graphene reinforced copper-based composite material provided by the invention can be used for obtaining a composite material with excellent strong plasticity and high strength and high conductivity.
Drawings
Fig. 1 shows the results of planar XRD scans of graphite papers used in examples 1, 2, 3 and 4 of the present invention.
Fig. 2 is a cross-sectional SEM photograph of the graphite paper used in examples 1, 2, 3, and 4 of the present invention.
Fig. 3 is an HRTEM photograph of graphene prepared by 50-pass cumulative rolling in example 1 of the present invention.
Fig. 4 is an HRTEM photograph of graphene prepared by 100-pass cumulative rolling in example 2 of the present invention.
Fig. 5 is an HRTEM photograph of graphene prepared by 200-pass cumulative rolling in example 3 of the present invention.
Fig. 6 is an HRTEM photograph of graphene prepared by 300-pass cumulative rolling in example 4 of the present invention.
Fig. 7 shows the comprehensive properties of the strength and plasticity of the graphene/copper composite material finally obtained by hot rolling in examples 2, 3 and 4 of the present invention, compared with the prior art.
Fig. 8 is a comparison of the strength and conductivity of the graphene/copper composite material obtained by the final hot rolling in examples 2, 3 and 4 of the present invention with those of the prior art.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples.
The passes described in the examples refer to the passes in which the graphite paper is rolled.
Example 1
(1) Graphite paper (0.2 g by mass) of size 40 x 15 x 0.2mm was taken, washed several times with acetone and deionized water and dried at below 60 ℃.
(2) A pure copper sheet (the copper sheet is marked as TU1) with the size of 100 × 20 × 1mm is taken and put into a 600 ℃ tube furnace which is filled with argon protective gas for calcination for 2h and annealing. The completely annealed pure copper sheet was subjected to surface treatment such as oxide film removal and degreasing, and the surface-treated pure copper sheet (mass: 17.6g) was folded in half.
(3) And (3) clamping the graphite paper pretreated in the step (1) in the middle of the pure copper sheet pretreated in the step (2), and pressing the folded part of the copper sheet to tightly wrap the graphite paper by the pure copper sheet.
(4) And carrying out multi-pass accumulated rolling on the pure copper sheet under the condition of no lubrication at room temperature. And (3) adopting an industrial rolling mill, wherein the rolling speed is 187mm/min, and the deformation of the sample in the thickness direction is controlled to be greater than or equal to 50% in each pass of rolling.
(5) When the graphite paper/copper composite sample is rolled for the 5 th pass, cracks appear on the surface of the pure copper sheet and gradually expand along with the increase of the rolling passes, the pure copper sheet and graphene are taken out together, the pure copper sheet and the graphene are cut into 5 samples with the same size, each sample is about 3.6g, one sample is clamped between the folded pure copper sheets (the pure copper sheet is completely annealed and subjected to surface treatment, the size is 100 x 20 x 1mm, and the mass is 17.7g), when the sample is rolled for the 30 th pass, microcracks appear on the surface of the pure copper sheet again, the pure copper sheet and the graphene are taken out together, the sample is cut into 6 samples with the similar size, each sample is about 3.4g, the samples are wrapped by the completely annealed and subjected to surface treatment (the size of the copper sheet is 100 x 20 x 1mm, and the mass is 18.2g), and the 50 th pass is continuously rolled.
Fig. 2 is a SEM picture of a cross section of the original graphite paper of the present invention, and it can be seen from fig. 2 that the graphite layers inside the original graphite paper are parallel to each other, and the thickness of each layer of graphite is in the micrometer range. Fig. 3 is an HRTEM photograph of graphene prepared by 50-pass cumulative rolling in example 1 of the present invention. As can be seen in fig. 3, the graphite paper is reduced to about 20 layers of graphite by 50 passes of cumulative lap rolling.
Example 2
(1) Graphite paper (0.2 g by mass) of size 40 x 15 x 0.2mm was taken, washed several times with acetone and deionized water and dried below 60 ℃.
(2) A pure copper sheet (the copper sheet is marked as TU1) with the size of 100 × 20 × 1mm is taken and put into a 600 ℃ tube furnace which is filled with argon protective gas for calcination for 2h and annealing. And (3) performing surface treatment such as oxide film removal, degreasing and the like on the fully annealed pure copper sheet, and folding the surface-treated pure copper sheet (with the mass of 17.6g) in half.
(3) And (3) clamping the graphite paper pretreated in the step (1) in the middle of the pure copper sheet pretreated in the step (2), and pressing the folded part of the copper sheet to tightly wrap the graphite paper by the copper sheet.
(4) And carrying out accumulative lap rolling on the pure copper sheet wrapped with the graphite paper under the condition of no lubrication at room temperature. An industrial rolling mill was used at a rolling speed of 187 mm/min. And controlling the deformation of the sample in the thickness direction to be greater than or equal to 50% in each pass of rolling.
(5) When the graphite paper/copper composite sample is rolled to the 10 th pass, cracks appear on the surface of the pure copper sheet and gradually expand along with the increase of the rolling times, the pure copper sheet and graphene are taken out, the pure copper sheet and the graphene are cut into 5 samples with the same size, each sample is about 3.6g, the samples are wrapped by the pure copper sheet (the size of the copper sheet is 100 x 20 x 1mm, the mass of the copper sheet is 17.7g) which is completely annealed and subjected to surface treatment, and rolling is continued until the graphite paper is thinned into few-layer graphene.
(6) When the graphene is rolled to the 30 th pass, microcracks appear on the surface of the pure copper sheet again, the pure copper sheet and the graphene are taken out, cut into 6 samples with the same size, each sample is about 3.6g, and wrapped by the pure copper sheet (with the size of 100 x 20 x 1mm and the mass of 18.2g) which is completely annealed and subjected to surface treatment, and the rolling is continued to the 100 th pass.
(7) And (3) carrying out one-time hot rolling (the hot rolling temperature is 600 ℃, and the heat preservation time is 10min) on the graphene/copper composite sample which is rolled by 100 times (the total times of rolling the graphite paper), so as to obtain the graphene/copper composite material.
Fig. 4 is an HRTEM photograph of graphene prepared by 100 passes of cumulative rolling in example 1 of the present invention. As can be seen from fig. 4, the graphite paper is thinned to 4 layers of graphene with 100 passes of cumulative pack rolling. The graphene/copper composite material obtained by carrying out one-time hot rolling on the graphene/copper composite sample subjected to the 100-time cold rolling has the strength of 616MPa, the ductility of 14.4% and the conductivity of 83% IACS.
Example 3
(1) Graphite paper (0.2 g by mass) of size 40 x 15 x 0.2mm was taken, washed several times with acetone and deionized water and dried at below 60 ℃.
(2) A pure copper sheet (the copper sheet is marked as TU1) with the size of 100 × 20 × 1mm is taken and put into a 600 ℃ tube furnace which is filled with argon protective gas for calcination for 2h and annealing. The completely annealed pure copper sheet was subjected to surface treatment such as oxide film removal and degreasing, and the surface-treated pure copper sheet (mass: 17.7g) was folded in half.
(3) And (3) clamping the graphite paper pretreated in the step (1) in the middle of the pure copper sheet pretreated in the step (2), and pressing the folded part of the copper sheet to tightly wrap the graphite paper by the pure copper sheet.
(4) And carrying out multi-pass accumulated rolling on the pure copper sheet under the condition of no lubrication at room temperature. And (3) adopting an industrial rolling mill, wherein the rolling speed is 187mm/min, and the deformation of the sample in the thickness direction is controlled to be greater than or equal to 50% in each pass of rolling.
(5) When the graphite paper/copper composite sample is rolled in the 10 th pass, cracks appear on the surface of the pure copper sheet and gradually expand along with the increase of the rolling passes, the pure copper sheet and graphene are taken out and cut into 6 samples with the same size, each sample is about 3.0g, one sample is clamped between the folded pure copper sheets (the pure copper sheet is completely annealed and subjected to surface treatment, the size is 100 x 20 x 1mm, and the mass is 17.7g), after the pure copper sheet is rolled to the 30 th pass, microcracks appear on the surface of the pure copper sheet again, the pure copper sheet and graphene are taken out and cut into 6 samples with similar sizes, each sample is about 3.5g, the samples are wrapped by the completely annealed and subjected to surface treatment (the size of the copper sheet is 100 x 20 x 1mm, and the mass is 18.2g), and the rolling is continued to the 200 th pass.
(6) And (3) carrying out one-time hot rolling (the hot rolling temperature is 600 ℃, and the heat preservation time is 10min) on the graphene/copper composite sample which is rolled by 200 times (the total times of rolling the graphite paper), so as to obtain the graphene/copper composite material.
Fig. 5 is an HRTEM photograph of graphene prepared by 200-pass cumulative rolling in example 3 of the present invention. As can be seen from fig. 5, after 200 passes of cumulative lap rolling, the graphite paper is thinned to 2-layer graphene. The graphene/copper composite material obtained by carrying out one-time hot rolling on the graphene/copper composite sample subjected to 200-time cold rolling has the strength of 646MPa, the ductility of 6.7% and the conductivity of 76% IACS.
Example 4
(1) Graphite paper (0.2 g by mass) of size 40 x 15 x 0.2mm was taken, washed several times with acetone and deionized water and dried below 60 ℃.
(2) A pure copper sheet (the copper sheet is marked as TU1) with the size of 100 × 20 × 1mm is taken and put into a 600 ℃ tube furnace which is filled with argon protective gas for calcination for 2h and annealing. And (3) performing surface treatment such as oxide film removal, degreasing and the like on the fully annealed pure copper sheet, and folding the surface-treated pure copper sheet (with the mass of 17.4g) in half.
(3) And (3) clamping the graphite paper pretreated in the step (1) in the middle of the pure copper sheet pretreated in the step (2), and pressing the folded part of the copper sheet to tightly wrap the graphite paper by the copper sheet.
(4) And carrying out accumulative lap rolling on the pure copper sheet wrapped with the graphite paper under the condition of no lubrication at room temperature. An industrial rolling mill was used at a rolling speed of 187 mm/min. And controlling the deformation of the sample in the thickness direction to be greater than or equal to 50% in each pass of rolling.
(5) When the graphite paper/copper composite sample is rolled to the 20 th pass, cracks appear on the surface of the pure copper sheet and gradually expand along with the increase of the rolling times, the pure copper sheet and graphene are taken out, the pure copper sheet and the graphene are cut into 5 samples with the same size, each sample is about 3.5g, the samples are wrapped by the pure copper sheet (the size of the copper sheet is 100 to 20 to 1mm, and the mass of the copper sheet is 17.7g) which is completely annealed and subjected to surface treatment, and the rolling is continued.
(6) When the sample is rolled to the 26 th pass, microcracks appear on the surface of the pure copper sheet again, the pure copper sheet and graphene are taken out, cut into 7 samples with similar sizes, each sample is about 3.0g, and the samples are wrapped by the pure copper sheet (with the size of 100 × 20 × 1mm and the mass of 18.2g) which is completely annealed and subjected to surface treatment respectively, and then the rolling is continued to the 300 th pass.
(7) And (3) carrying out one-time hot rolling (the hot rolling temperature is 600 ℃, and the heat preservation time is 10min) on the graphene/copper composite sample which is rolled by 300 times (the total times of rolling the graphite paper), so as to obtain the graphene/copper composite material.
Fig. 1 is a cross-sectional SEM picture of the graphite paper raw material of the present invention, and it can be seen from fig. 2 that the graphite layers inside the graphite paper raw material are parallel to each other, and the thickness of each layer of graphite is in the micrometer scale, and is not in the form of graphene. Fig. 6 is an HRTEM photograph of graphene prepared by 300-pass cumulative rolling in example 3 of the present invention. As can be seen from fig. 6, after 300 passes of cumulative rolling, the graphite paper can be thinned to graphene with a single layer thickness. The graphene/copper composite material obtained by carrying out one-time hot rolling on the graphene/copper composite sample subjected to 300-time cold rolling has the strength of 682MPa, the ductility of 9.4% and the conductivity of 72% IACS.
Comparing example 2, example 3 and example 4 of the present invention, it can be found that the graphite paper can be thinned into few layers of high quality graphene by multi-pass cumulative overlapping rolling, and the number of graphene layers prepared is lower as the number of rolling passes increases. As can be seen from fig. 7 and 8, the toughness, the strength and the conductivity of the graphene/copper composite material obtained by directly using the prepared graphene as a reinforcement are obviously superior to those of other research results, and the method for preparing the graphene in situ in the invention is further laterally proved to have high efficiency.
Table 1. the reference documents [1-17] in FIG. 7 are comprehensive properties of strength and elongation of copper/graphene composite materials prepared by other researchers
Table 2. the reference in FIG. 8 [1,4-6,11,13,18] shows the comprehensive properties of strength and conductivity of copper/graphene composite materials prepared by other researchers
The present invention is not limited to the above-described embodiments, and it will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and such modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Claims (9)
1. A preparation method of graphene is characterized by comprising the following steps:
(1) annealing the pure copper sheet, and performing surface treatment on the annealed pure copper sheet to remove impurities on the surface of the pure copper sheet for later use;
(2) placing graphite paper with thickness less than or equal to 0.5mm and (002) texture between two pure copper sheets at room temperature, and starting rolling after the pure copper sheets clamp the graphite paper;
(3) after rolling for 5-30 times, taking out the pure copper sheets and the graphite paper therein, cutting the pure copper sheets and the graphite paper into small samples, placing the small samples between two annealed pure copper sheets, and continuing rolling;
(4) and (4) repeating the step (3) until the cumulative rolling pass of the graphite paper is more than 100 times, thus obtaining the graphene with the number of layers less than or equal to 4.
2. The method of claim 1, wherein: the graphite paper is pretreated before use in the following way: the graphite paper is washed with acetone and deionized water several times and then dried at a temperature below 60 ℃.
3. The method of claim 1, wherein: the deformation amount of the control sample in the thickness direction per rolling is 50% or more.
4. The method of claim 1, wherein: and (4) controlling the accumulated rolling pass to be more than or equal to 200, and obtaining the graphene product with the layer number of 2.
5. The method of claim 1, wherein: and (4) controlling the accumulated rolling pass to be more than or equal to 300 to obtain the graphene product with the layer number of 1.
6. The method of claim 1, wherein: and (4) the cumulative rolling pass of the graphite paper in the step (4) is 100-300 passes.
7. The method of claim 1, wherein: the machine used for rolling is an industrial rolling mill, and the rolling speed is 100-300 mm/min.
8. The preparation method of the in-situ graphene reinforced copper-based composite material is characterized by comprising the following steps of:
(1) annealing the pure copper sheet, and performing surface treatment on the annealed pure copper sheet to remove impurities on the surface of the pure copper sheet for later use;
(2) placing graphite paper with the thickness less than or equal to 0.5mm between two pure copper sheets at room temperature, and starting rolling after the pure copper sheets clamp the graphite paper;
(3) after rolling for 5-30 times, taking out the pure copper sheets and the graphite paper therein, cutting the pure copper sheets and the graphite paper into small samples, placing the small samples between two pure copper sheets, and continuing rolling;
(4) repeating the step (3) until the cumulative rolling pass of the graphite paper is more than 100 times;
(5) and (4) placing the sample obtained in the step (4) into a muffle furnace at 500-700 ℃ for heat preservation, and then carrying out hot rolling for one pass.
9. The method of claim 8, wherein: the hot rolling temperature is 600 ℃, and the heat preservation time is 10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911034547.2A CN110923591B (en) | 2019-10-29 | 2019-10-29 | Preparation method and application of graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911034547.2A CN110923591B (en) | 2019-10-29 | 2019-10-29 | Preparation method and application of graphene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110923591A true CN110923591A (en) | 2020-03-27 |
| CN110923591B CN110923591B (en) | 2020-09-22 |
Family
ID=69849693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911034547.2A Active CN110923591B (en) | 2019-10-29 | 2019-10-29 | Preparation method and application of graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110923591B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198840A (en) * | 2021-04-22 | 2021-08-03 | 武汉大学 | Method for preparing graphene from carbon nano tube and application of graphene |
| CN113695394A (en) * | 2021-08-31 | 2021-11-26 | 全球能源互联网研究院有限公司 | Graphene copper-based composite material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1796308A1 (en) * | 1991-03-26 | 1993-02-23 | Inst Metallurg Im F N Tavadze | Rolling method |
| CA2783939A1 (en) * | 2009-09-17 | 2011-03-24 | Bayer International Sa | A compound material comprising a metal and nanoparticles |
| CN106270509A (en) * | 2016-08-08 | 2017-01-04 | 武汉大学 | A kind of preparation method of Zinc oxide particles reinforced aluminum matrix composites |
| CN106756195A (en) * | 2017-01-22 | 2017-05-31 | 武汉大学 | A kind of Graphene enhancing Cu-base composites and its preparation method and application |
| CN110125181A (en) * | 2018-02-09 | 2019-08-16 | 常州第六元素材料科技股份有限公司 | Roll-bonding prepares the method and its alkene alloy of alkene alloy |
| CN110125179A (en) * | 2018-02-09 | 2019-08-16 | 常州第六元素材料科技股份有限公司 | Graphene composition metal and preparation method thereof |
-
2019
- 2019-10-29 CN CN201911034547.2A patent/CN110923591B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1796308A1 (en) * | 1991-03-26 | 1993-02-23 | Inst Metallurg Im F N Tavadze | Rolling method |
| CA2783939A1 (en) * | 2009-09-17 | 2011-03-24 | Bayer International Sa | A compound material comprising a metal and nanoparticles |
| CN106270509A (en) * | 2016-08-08 | 2017-01-04 | 武汉大学 | A kind of preparation method of Zinc oxide particles reinforced aluminum matrix composites |
| CN106756195A (en) * | 2017-01-22 | 2017-05-31 | 武汉大学 | A kind of Graphene enhancing Cu-base composites and its preparation method and application |
| CN110125181A (en) * | 2018-02-09 | 2019-08-16 | 常州第六元素材料科技股份有限公司 | Roll-bonding prepares the method and its alkene alloy of alkene alloy |
| CN110125179A (en) * | 2018-02-09 | 2019-08-16 | 常州第六元素材料科技股份有限公司 | Graphene composition metal and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113198840A (en) * | 2021-04-22 | 2021-08-03 | 武汉大学 | Method for preparing graphene from carbon nano tube and application of graphene |
| CN113695394A (en) * | 2021-08-31 | 2021-11-26 | 全球能源互联网研究院有限公司 | Graphene copper-based composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110923591B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111145960B (en) | High-strength high-conductivity copper-based composite material and preparation method thereof | |
| CN110923591B (en) | Preparation method and application of graphene | |
| CN110000388B (en) | Preparation method of novel graphene nanosheet reinforced metal-based composite material | |
| CN108396168A (en) | A kind of preparation method of high-strength highly-conductive creep resistant graphene enhancing aluminum alloy materials | |
| CN111349905B (en) | Preparation method of enhanced copper-based composite wire | |
| CN108555039B (en) | Preparation method of copper/steel laminated composite material and composite material prepared by preparation method | |
| CN110788144B (en) | Metallic copper-graphene laminated composite material and preparation method and device thereof | |
| CN1100153C (en) | Two phase titanium aluminide alloy | |
| CN114953620A (en) | Preparation method of graphene-copper composite material combining hot-pressing sintering and chemical vapor deposition | |
| CN110576072A (en) | Preparation method of multilayer pure copper-brass composite board | |
| CN109825785B (en) | Preparation method of industrial pure titanium with heterogeneous layered structure | |
| EP2778128A1 (en) | Method of thermal reduction of graphene oxide | |
| WO2019224578A1 (en) | A method for the manufacture of graphene oxide from electrode graphite scrap | |
| CN111375713A (en) | Rotary swaging preparation method of high-strength aluminum conductor | |
| CN112342431B (en) | High-thermal-stability equiaxial nanocrystalline Ti6Al4V-Cu alloy and preparation method thereof | |
| CN112063892B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Zr-Mn alloy and preparation method thereof | |
| CN112342433B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Zr-W alloy and preparation method thereof | |
| CN110257665B (en) | Preparation method of pure copper-brass composite wire with soft/hard filamentous structure | |
| CN112063890B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Ag alloy and preparation method thereof | |
| CN114261155B (en) | Magnesium-titanium laminated plate with good strong plasticity and preparation method thereof | |
| CN112342434B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Mn alloy and preparation method thereof | |
| CN112251644B (en) | High-thermal-stability equiaxial nanocrystalline Ti6Al4V-Ag alloy and preparation method thereof | |
| CN112251638B (en) | High-thermal-stability equiaxial nanocrystalline Ti-Cu alloy and preparation method thereof | |
| CN112195367B (en) | High-thermal-stability equiaxed nanocrystalline Ti6Al4V-Co alloy and preparation method thereof | |
| CN112322930B (en) | Low-temperature superplastic titanium alloy plate, bar and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |