CN111041426B - Graphene-aluminum composite material and preparation method thereof - Google Patents
Graphene-aluminum composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
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- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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Abstract
The invention relates to a preparation method of a graphene-aluminum composite material, which comprises the following steps: providing graphene aerogel, and forming an aluminum film on the surface of the graphene aerogel by adopting a vacuum evaporation method; stirring the graphene aerogel with the aluminum film formed on the surface to obtain graphene powder with the aluminum film formed on the surface; and compounding the graphene powder with the aluminum film formed on the surface and the aluminum matrix by adopting a stirring casting method. The invention further relates to a graphene-aluminum composite material and a cable or wire comprising the graphene-aluminum composite material.
Description
Technical Field
The invention relates to the technical field of metal matrix composite materials, in particular to a graphene-aluminum composite material and a preparation method thereof.
Background
Graphene is a novel two-micron nanocrystalline material and has excellent electrical properties, mechanical properties and the like. The performance of graphene is considered to be an ideal reinforcing phase of the metal matrix composite, while the traditional reinforcing mode of aluminum and aluminum alloy is difficult to obviously improve, and the graphene reinforced aluminum matrix composite becomes an effective way for breaking the impasse. The existing process for preparing the graphene aluminum-based composite material is a powder metallurgy method, which can realize the uniform distribution of graphene in an aluminum matrix, but has a long preparation period. The problem of uniform mixing of graphene in an aluminum matrix becomes an important reason for limiting the process development of the graphene reinforced aluminum matrix due to the extremely poor wettability between the non-metallic graphene and the metal aluminum, and therefore, a preparation method of a graphene aluminum matrix composite with a short preparation period and simplicity and effectiveness is urgently needed.
Disclosure of Invention
Based on this, it is necessary to provide a graphene-aluminum composite material, a method for preparing the same, and a cable or wire including the same, aiming at the problems that the preparation period is long and graphene and an aluminum matrix cannot be uniformly mixed.
The invention provides a preparation method of a graphene-aluminum composite material, which comprises the following steps:
providing graphene aerogel, and forming an aluminum film on the surface of the graphene aerogel by adopting a vacuum evaporation method;
stirring the graphene aerogel with the aluminum film formed on the surface to obtain graphene powder with the aluminum film formed on the surface; and
and compounding the graphene powder with the aluminum film formed on the surface and the aluminum matrix by adopting a stirring casting method.
In one embodiment, the step of forming an aluminum film on the surface of the graphene aerogel by using a vacuum evaporation method includes:
carrying out ion bombardment on the graphene aerogel in a vacuum state, wherein the bombardment voltage is 200-500V, and the bombardment time is 15-30 min;
and adjusting the temperature of the evaporation source to 1200-1300 ℃ to gasify the aluminum, and depositing the gasified aluminum particles on the graphene aerogel to form an aluminum film.
In one embodiment, the thickness of the aluminum film formed on the surface of the graphene aerogel is 10 μm to 100 μm.
In one embodiment, the graphene aerogel has a specific surface area of 100m2/g～400m2The pore diameter is 5nm to 15 nm.
In one embodiment, the graphene aerogel is formed by adopting a graphene oxide aqueous solution through an ice template method, wherein the ice template method comprises a step of carrying out vacuum freeze drying on the graphene oxide aqueous solution and a step of carrying out vacuum heat treatment reduction on the graphene oxide aqueous solution, the freeze drying temperature is-50 ℃ to-75 ℃, the freeze drying time is 20h to 30h, the heat treatment reduction temperature is 1500 ℃ to 2500 ℃, and the heat treatment reduction time is 2h to 4 h.
In one embodiment, the stirring speed is 450rpm/min to 500 rpm/min.
In one embodiment, the step of compounding the graphene powder with the aluminum film formed on the surface thereof and the aluminum substrate by using a stir casting method includes:
heating and melting the aluminum matrix at 650-800 ℃ to form aluminum liquid;
and adding the graphene powder with the aluminum film formed on the surface into the aluminum liquid, stirring at the rotating speed of 160-200 rpm/min for 20-40 min, and cooling and solidifying.
In one embodiment, the mass ratio of the graphene powder to the aluminum matrix is (0.003-0.006): 1.
in one embodiment, the aluminum matrix is high purity aluminum or an aluminum alloy.
In one embodiment, the preparation method of the graphene-aluminum composite material further includes a step of performing vacuum evaporation on the graphene powder with the aluminum film formed thereon again.
The invention also provides a graphene-aluminum composite material prepared by the preparation method of the graphene-aluminum composite material.
The invention further provides a cable or wire comprising the graphene-aluminum composite material.
According to the preparation method of the graphene-aluminum composite material, the aluminum film is formed on the surface of the graphene aerogel with the three-dimensional network structure by adopting a vacuum evaporation method, the graphene sheets which are mutually overlapped in the graphene aerogel are dispersed by stirring to form the graphene powder, and the vacuum evaporation aluminum film cannot fall off by stirring, so that the graphene powder with the aluminum film formed on the surface can be effectively prepared by stirring, and then the graphene powder with the aluminum film formed on the surface is compounded with the aluminum matrix by a stirring casting method to obtain the graphene-aluminum composite material. By adopting the technical means of the invention, the graphene powder with the aluminum film formed on the surface can be effectively obtained, and due to the existence of the surface aluminum film, the wettability between the graphene powder and the aluminum matrix is greatly improved, and the uniform distribution of graphene in the aluminum matrix is further realized by a stirring casting method. The method for preparing the graphene-aluminum composite material is simple to operate and short in preparation period, and solves the problems that graphene is easy to agglomerate and difficult to disperse.
Drawings
Fig. 1 is a scanning electron microscope photograph of the graphene-aluminum composite material prepared in example 1 of the present invention;
fig. 2 is a scanning electron microscope photograph of the graphene-aluminum composite material prepared in comparative example 1 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The embodiment of the invention provides a preparation method of a graphene-aluminum composite material, which comprises the following steps:
s10, providing graphene aerogel, and forming an aluminum film on the surface of the graphene aerogel by adopting a vacuum evaporation method;
s20, stirring the graphene aerogel with the aluminum film formed on the surface to obtain graphene powder with the aluminum film formed on the surface;
and S30, compounding the graphene powder with the aluminum film formed on the surface and the aluminum matrix by adopting a stirring casting method.
According to the preparation method of the graphene-aluminum composite material provided by the embodiment of the invention, the aluminum film is formed on the surface of the graphene aerogel with the three-dimensional network structure by adopting a vacuum evaporation method, the graphene sheets which are mutually overlapped in the graphene aerogel are dispersed by stirring to form the graphene powder, and the vacuum evaporation aluminum film is not dropped by stirring, so that the graphene powder with the aluminum film formed on the surface can be effectively prepared by stirring, and then the graphene powder with the aluminum film formed on the surface is compounded with the aluminum matrix by a stirring casting method to obtain the graphene-aluminum composite material. By adopting the technical means of the invention, the graphene powder with the aluminum film formed on the surface can be effectively obtained, and due to the existence of the surface aluminum film, the wettability between the graphene powder and the aluminum matrix is greatly improved, and the uniform distribution of graphene in the aluminum matrix is further realized by a stirring casting method. The method for preparing the graphene-aluminum composite material is simple to operate and short in preparation period, and solves the problems that graphene is easy to agglomerate and difficult to disperse.
In step S10, the graphene aerogel is a three-dimensional network structure in which graphene sheets formed under certain conditions are overlapped and stacked with each other using graphene oxide as a precursor. In some embodiments, the graphene aerogel has a specific surface area of 100m2/g～400m2The pore diameter is 5nm to 15 nm.
The graphene aerogel may be formed by an in situ self-assembly method or a template method. Preferably, the graphene aerogel is formed by an ice template method using a graphene oxide aqueous solution. The graphene oxide in the graphene oxide aqueous solution is a single-layer or few-layer graphene oxide, and the oxygen content of the graphene oxide aqueous solution can be 30-50% by mass.
The ice template method comprises a step of carrying out vacuum freeze drying on the graphene oxide aqueous solution and a step of carrying out vacuum heat treatment reduction. In some embodiments, the temperature of the freeze-drying may be-50 ℃ to-75 ℃, and the freeze-drying time may be 20 hours to 30 hours. The temperature of freeze drying can be independently selected from-55 deg.C, -60 deg.C, -65 deg.C or-70 deg.C. In some embodiments, the temperature for the heat treatment reduction may be 1500 ℃ to 2500 ℃, and the heat treatment reduction time may be 2h to 4 h. The temperature for the heat treatment reduction may be selected independently from 1600 ℃, 1700 ℃, 1800 ℃, 1900 ℃, 2000 ℃, 2100 ℃, 2200 ℃, 2300 ℃ and 2400 ℃. Both the freeze-drying temperature and the heat treatment reduction temperature affect the overlapping stacking of graphene sheets in the graphene aerogel. The addition amount of different graphene oxides has a relatively large influence on the morphology of the graphene aerogel, and in some embodiments, the concentration of the graphene oxide aqueous solution is 3mg/ml to 6 mg/ml.
In an embodiment, the step of forming an aluminum film on the graphene aerogel in step S10 by using a vacuum evaporation method includes:
s11, performing ion bombardment on the graphene aerogel in a vacuum state, wherein the bombardment voltage is 200-500V, and the bombardment time is 15-30 min;
and S12, adjusting the temperature of the evaporation source to 1200-1300 ℃, gasifying aluminum, and depositing the gasified aluminum particles on the graphene aerogel to form an aluminum film.
According to the graphene aerogel with the aluminum film formed on the surface, which is prepared by the vacuum evaporation method, the aluminum film is in an atom attachment state under the action of ion bombardment and aluminum particles, and the aluminum film and the graphene are chemically adsorbed, so that the adhesion is strong. The graphene particles are difficult to fall off in the stirring and stirring casting processes, and the formed composite material is difficult to generate particle segregation (particle segregation is particle shift caused by the interaction of the particles and a solidification interface, and the particles are shifted to a final solidification area by the solidification interface to form particle segregation).
In some embodiments, the bombardment voltage in step S11 can also be independently selected from 250V, 300V, 350V, 400V, 450V.
In some embodiments, the bombardment time in step S11 can also be independently selected from 16min, 17min, 18min, 19min, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, and 29 min.
In some embodiments, the evaporation source temperature in step S12 can be selected from 1210 deg.C, 1220 deg.C, 1230 deg.C, 1240 deg.C, 1250 deg.C, 1260 deg.C, 1270 deg.C, 1280 deg.C, 1290 deg.C.
In one embodiment, step S11 further includes turning on the diffusion pump to achieve a vacuum level of 5 × 10 in the vacuum chamber-3Pa～8×10-3Pa, and baking the graphene powder after ion bombardment, aiming atAnd removing gas in the graphene to promote the deposition of aluminum particles on the surface of the graphene powder. In one embodiment, the temperature for baking the ion bombarded graphene powder is 80-150 ℃.
In one embodiment, the thickness of the aluminum film formed on the surface of the graphene aerogel is 10 micrometers to 100 micrometers.
Step S20, dispersing the overlapped and stacked graphene sheets in the graphene aerogel by adopting magnetic stirring to form graphene powder. In one embodiment, the magnetic stirring speed is 450rpm/min to 500 rpm/min. In some embodiments, the magnetic stirring speed can also be selected from 460rpm/min, 470rpm/min, 480rpm/min, 490 rpm/min. The aluminum film is easy to fall off due to the fact that the magnetic stirring speed is too high, and graphene sheets overlapped and stacked in the graphene aerogel cannot be dispersed due to the fact that the magnetic stirring speed is too low.
In an embodiment, the step S30 of compounding the graphene powder with the aluminum film formed on the surface thereof and the aluminum matrix by using a stir casting method includes:
s31, heating and melting the aluminum matrix at 650-800 ℃ to form aluminum liquid;
and S32, adding the graphene powder with the aluminum film formed on the surface into the molten aluminum liquid obtained in the step S31, stirring at the rotating speed of 160-200 rpm/min for 20-40 min, and cooling and solidifying.
The temperature of the aluminum matrix for heating and melting influences the viscosity of the aluminum liquid, and further influences the distribution of the graphene powder with the aluminum film in the aluminum matrix. In some embodiments, the temperature at which the aluminum matrix is heated to melt can also be independently selected to be 680 ℃, 700 ℃, 720 ℃, 750 ℃, 780 ℃.
In some embodiments, the rotation speed in step S32 can also be independently selected from 170rpm/min, 180rpm/min and 190 rpm/min.
In step S31, the aluminum matrix may be high purity aluminum (aluminum content of 99.9 wt% or more) or an aluminum alloy.
The step of cooling and solidifying in the step S32 may be performed in a metal mold or a water-cooled mold, so as to increase the cooling and solidifying speed of the composite material, which is beneficial to uniform distribution of the graphene powder particles in the aluminum matrix.
In one embodiment, in order to prevent the gas from being involved in the stirring process to form a loose structure, the stirring process in step S32 is performed under vacuum or inert gas protection.
In an embodiment, after the step S20 and before the step S30, the method further includes a step of performing vacuum evaporation on the graphene powder with the aluminum film formed thereon again, so as to further improve the thickness and uniformity of the aluminum film on the surface of the graphene powder.
In some embodiments, the mass ratio of the graphene powder to the aluminum matrix may be (0.003-0.006): 1, 0.0035:1, 0.004:1, 0.0045:1, 0.005:1, 0.0055:1 can also be selected.
The following are specific examples:
example 1
(1) And (2) freeze-drying 100mL of graphene oxide aqueous solution with the concentration of 5mg/mL at the temperature of minus 50 ℃ for 20h, cutting the prepared graphene oxide aerogel into small blocks with the size of 50 multiplied by 50mm, and reducing for 2h in a vacuum environment at 2000 ℃ to obtain the graphene aerogel.
(2) And (2) putting the graphene aerogel prepared in the step (1) into vacuum coating equipment, vacuumizing a vacuum chamber until the vacuum degree is 0.1Pa, and performing ion bombardment on a sample at the voltage of 200V for 30 min. The diffusion pump was turned on to make the vacuum chamber in a high vacuum state with a pressure of 5X 10-3And when Pa, baking the graphene aerogel so as to further remove the gas in the graphene aerogel. Preheating an evaporation source, adjusting the voltage to enable the temperature to reach 700 ℃, melting aluminum strips in the evaporation source into a molten state, adjusting the power to 500W, adjusting the temperature to reach 1250 ℃, enabling the aluminum strips in the evaporation source to volatilize, and performing evaporation for 5min to obtain the graphene aerogel with the aluminum film formed on the surface.
(3) And (3) putting the graphene aerogel with the aluminum film formed on the surface in the step (2) into a sealed magnetic stirrer, and crushing the graphene aerogel through magnetic stirring, wherein the rotating speed of the stirrer is 500rpm/min, and the stirring time is 10min, so that the graphene powder with the aluminum film formed on the surface is obtained.
(4) Weighing 100g of high-purity aluminum ingot, heating and melting the high-purity aluminum ingot in a crucible of a stirring casting furnace, wherein the heating power is 300W, the temperature in the crucible is 750 ℃, after the aluminum ingot is completely melted, adding the graphene powder with the aluminum film formed on the surface in the step (3) into the molten aluminum liquid, stirring at 180rpm/min for 30min, pouring the stirred aluminum liquid into a water-cooled mold, cooling the mold to room temperature, taking out the prepared graphene aluminum composite material, and performing metallographic structure observation, wherein the metallographic structure observation is to cut the prepared sample into small blocks of 10 multiplied by 10mm by linear cutting, after one surface is selected, hand polishing is carried out on 80#, 150#, 300#, 500#, 800#, 1000#, 1500# and 3000# sandpaper respectively, then, mechanical polishing was performed on the flannelette, and after drying the sample, metallographic structure observation was performed by a scanning electron microscope. The scanning electron microscope photograph of the graphene-aluminum composite material prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that graphene is uniformly distributed in the aluminum metal phase.
Example 2
The same as example 1 except that the concentration of the aqueous graphene oxide solution in step (1) was 3 mg/ml. The scanning electron microscope photograph of the graphene aluminum composite material prepared in this example shows that the graphene can be uniformly distributed in the aluminum metal phase.
Example 3
The same as example 1 except that the concentration of the aqueous graphene oxide solution in step (1) was 4 mg/ml. The scanning electron microscope photograph of the graphene-aluminum composite material prepared in this example shows that graphene can be uniformly distributed in the aluminum metal phase.
Example 4
The same as example 1 except that the concentration of the aqueous graphene oxide solution in step (1) was 6 mg/ml. The scanning electron microscope photograph of the graphene-aluminum composite material prepared in this example shows that graphene can be uniformly distributed in the aluminum metal phase.
Comparative example 1
Weighing 100g of high-purity aluminum ingot, heating and melting the high-purity aluminum ingot in a crucible of a stirring casting furnace, wherein the heating power is 300W, the temperature in the crucible is 750 ℃, after the aluminum ingot is completely melted, adding graphene powder without an aluminum film into molten aluminum, stirring the mixture at 180rpm/min for 30min, pouring the stirred aluminum liquid into a water-cooled mold, cooling the temperature of the mold to room temperature, taking out the prepared graphene-aluminum composite material, and observing a metallographic structure, wherein a scanning electron microscope photo of the graphene-aluminum composite material prepared by the comparative example is shown in figure 2, and as can be seen from figure 2, almost no graphene exists in the aluminum metallic phase.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The preparation method of the graphene-aluminum composite material is characterized by comprising the following steps:
providing graphene aerogel, and forming an aluminum film on the surface of the graphene aerogel by adopting a vacuum evaporation method;
stirring the graphene aerogel with the aluminum film formed on the surface to obtain graphene powder with the aluminum film formed on the surface; and
and compounding the graphene powder with the aluminum film formed on the surface and the aluminum matrix by adopting a stirring casting method.
2. The preparation method of the graphene-aluminum composite material according to claim 1, wherein the step of forming the aluminum film on the surface of the graphene aerogel by using a vacuum evaporation method comprises:
carrying out ion bombardment on the graphene aerogel in a vacuum state, wherein the bombardment voltage is 200-500V, and the bombardment time is 15-30 min;
and adjusting the temperature of the evaporation source to 1200-1300 ℃ to gasify the aluminum, and depositing the gasified aluminum particles on the graphene aerogel to form an aluminum film.
3. The preparation method of the graphene-aluminum composite material according to claim 1 or 2, wherein the thickness of the aluminum film formed on the surface of the graphene aerogel is 10 μm to 100 μm.
4. The preparation method of the graphene-aluminum composite material according to claim 1, wherein the graphene aerogel has a specific surface area of 100m2/g～400m2The pore diameter is 5nm to 15 nm.
5. The preparation method of the graphene aluminum composite material according to claim 1, wherein the graphene aerogel is formed by an ice template method by using a graphene oxide aqueous solution, the ice template method comprises a step of carrying out vacuum freeze drying and a step of carrying out vacuum heat treatment reduction on the graphene oxide aqueous solution, the freeze drying temperature is-50 ℃ to-75 ℃, the freeze drying time is 20h to 30h, the heat treatment reduction temperature is 1500 ℃ to 2500 ℃, the heat treatment reduction time is 2h to 4h, and the concentration of the graphene oxide aqueous solution is 3mg/ml to 6 mg/ml.
6. The method for preparing the graphene aluminum composite material according to claim 1, wherein the stirring speed is 450rpm/min to 500 rpm/min.
7. The method for preparing the graphene-aluminum composite material according to claim 1, wherein the step of compounding the graphene powder with the aluminum film formed on the surface thereof and the aluminum matrix by using a stirring casting method comprises:
heating and melting the aluminum matrix at 650-800 ℃ to form aluminum liquid;
and adding the graphene powder with the aluminum film formed on the surface into the aluminum liquid, stirring at the rotating speed of 160-200 rpm/min for 20-40 min, and cooling and solidifying.
8. The preparation method of the graphene-aluminum composite material according to claim 1, wherein the mass ratio of the graphene powder to the aluminum matrix is (0.003-0.006): 1.
9. the method for preparing a graphene aluminum composite material according to claim 1, wherein the aluminum matrix is high-purity aluminum or an aluminum alloy.
10. The method according to claim 1, further comprising a step of performing vacuum evaporation on the graphene powder with the aluminum film formed thereon again.
11. The graphene-aluminum composite material prepared by the method for preparing the graphene-aluminum composite material according to any one of claims 1 to 10.
12. A cable or wire comprising the graphene aluminum composite material of claim 11.
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| CN106480434A (en) * | 2015-08-26 | 2017-03-08 | 中国科学院宁波材料技术与工程研究所 | A kind of chemical plating Graphene and preparation method thereof and a kind of metal-base composites |
| CN106544539A (en) * | 2015-09-16 | 2017-03-29 | 弘大科技（北京）股份公司 | A kind of aeroge-metallic composite and its preparation method and application |
| CN107099692A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof |
| CN107502772A (en) * | 2017-07-17 | 2017-12-22 | 无锡吉仓纳米材料科技有限公司 | A kind of preparation method for casting graphene/aluminum alloy composite materials and casting graphene/aluminum alloy composite materials |
| CN108103485A (en) * | 2017-12-18 | 2018-06-01 | 西安理工大学 | A kind of preparation method in graphene surface clad copper or nickel |
| CN110317977A (en) * | 2019-01-17 | 2019-10-11 | 杭州电缆股份有限公司 | A kind of preparation method of graphene aerogel aluminium composite material |
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