CN111101172B - Graphene-aluminum composite material and preparation method thereof - Google Patents
Graphene-aluminum composite material and preparation method thereof Download PDFInfo
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- CN111101172B CN111101172B CN201911415918.1A CN201911415918A CN111101172B CN 111101172 B CN111101172 B CN 111101172B CN 201911415918 A CN201911415918 A CN 201911415918A CN 111101172 B CN111101172 B CN 111101172B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
Abstract
The invention relates to a preparation method of a graphene-aluminum composite material, which comprises the following steps: providing graphene aerogel and placing the graphene aerogel serving as a cathode in molten electrolytic salt, wherein the anode is metal aluminum, and the electrolytic current is 250-350 mA. The invention also 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
The graphene aluminum-based composite material has high strength, high electrical conductivity, high thermal conductivity and high wear resistance, and is a key material for the current material research, but due to the inherent wettability difference between metal and nonmetal, graphene is difficult to be uniformly distributed in an aluminum matrix, and in order to achieve a good graphene dispersion uniformity, a large amount of time is usually consumed for carrying out a mixing process; in addition, the traditional preparation method can easily lead the graphene and the aluminum matrix to generate a carbon aluminum compound Al in the high-temperature process of the forming stage4C3The substance is easy to hydrolyze in air, and the generated brittle phase seriously influences the strength of the composite material.
Therefore, a method for preparing the graphene aluminum matrix composite material with high efficiency and without high-temperature molding is urgently needed to be found.
Disclosure of Invention
Based on the above, it is necessary to provide a graphene aluminum composite material, a preparation method thereof, and a cable or wire comprising the graphene aluminum composite material, aiming at the problems of long preparation time and high temperature molding.
The invention provides a preparation method of a graphene-aluminum composite material, which comprises the following steps:
providing graphene aerogel and placing the graphene aerogel serving as a cathode in molten electrolytic salt, wherein the anode is metal aluminum, and the electrolytic current is 250-350 mA.
In one embodiment, the graphene aerogel is formed by an ice template method.
In one embodiment, the method for forming graphene aerogel by using the ice template method comprises the following steps:
carrying out vacuum freeze drying on the graphene oxide aqueous solution, wherein the freeze drying temperature is-50 ℃ to-75 ℃, and the freeze drying time is 20h to 30 h; and
and (3) performing vacuum heat treatment reduction, wherein the heat treatment temperature is 1500-2500 ℃, and the heat treatment reduction time is 2-4 h.
In one embodiment, the graphene aerogel has a density of 50mg/cm3～150mg/cm3。
In one embodiment, the graphene aerogel has a pore diameter of 5nm to 15nm and a specific surface area of 100m2/g～400m2/g。
In one embodiment, the electrolytic salt comprises one or more of sodium chloride, potassium chloride, and aluminum chloride.
In one embodiment, the electrolytic salts are sodium chloride, potassium chloride, and aluminum chloride.
In one embodiment, the mass ratio of sodium chloride, potassium chloride and aluminum chloride in the electrolytic salt is 1: (1-3): (6-10).
The invention also provides a graphene-aluminum composite material prepared by the preparation method of the graphene-aluminum composite material.
In one embodiment, the graphene hydrogel comprises a graphene hydrogel matrix and an aluminum-plated layer formed on the graphene hydrogel matrix, wherein the aluminum-plated layer has a thickness of 50 μm-1 mm.
The present invention further provides a cable or wire comprising the graphene aluminum composite material according to claim 9 or 10.
According to the preparation method of the graphene-aluminum composite material, provided by the invention, the graphene aerogel is used as a cathode, the metal aluminum is used as an anode, the cathode and the anode are placed in molten electrolytic salt, and electrolysis is carried out under the electrolytic current of 250 mA-350 mA to obtain the graphene-aluminum composite material. According to the preparation method, the graphene and the aluminum matrix are not required to be compounded at a high temperature, aluminum is directly formed on the surface of the graphene aerogel to form the aluminum-plated layer, the binding force between the aluminum-plated layer and the graphene aerogel in the graphene aluminum composite material obtained by the method is better, and the aluminum-plated layer is more uniformly distributed on the surface of the graphene aerogel, so that the graphene aluminum composite material has better electrical conductivity and mechanical strength.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. 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:
providing graphene aerogel and placing the graphene aerogel serving as a cathode in molten electrolytic salt, wherein the anode is metal aluminum, and the electrolytic current is 250-350 mA.
According to the preparation method of the graphene-aluminum composite material provided by the embodiment of the invention, the graphene aerogel is used as a cathode, the metal aluminum is used as an anode, the cathode and the anode are placed in molten electrolytic salt, and electrolysis is carried out under the electrolytic current of 250 mA-350 mA to obtain the graphene-aluminum composite material. According to the preparation method, the graphene and the aluminum matrix are not required to be compounded at a high temperature, aluminum is directly formed on the surface of the graphene aerogel to form the aluminum-plated layer, the binding force between the aluminum-plated layer and the graphene aerogel in the graphene aluminum composite material obtained by the method is better, and the aluminum-plated layer is more uniformly distributed on the surface of the graphene aerogel, so that the graphene aluminum composite material has better electrical conductivity and mechanical strength.
In some embodiments, the electrolysis current can also be selected from 260mA, 270mA, 280mA, 290mA, 300mA, 310mA, 320mA, 330mA, 340 mA.
In some embodiments, the electrolysis time may be 40min to 80min, and may be 45min, 50min, 55min, 60min, 65min, 70min, or 75 min.
The graphene aerogel can be formed by in-situ self-assembly, a template method, chemical crosslinking or the like. Preferably, the graphene aerogel is formed by an ice template method.
The method for forming the graphene aerogel by the ice template method may include a step of subjecting the graphene oxide aqueous solution to vacuum freeze-drying and a step of vacuum heat treatment reduction. The concentration of the graphene oxide solution is more than or equal to 3 mg/mL. 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. 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 ℃. The freeze-drying temperature and the heat treatment reduction temperature both affect the overlapping and stacking of graphene sheets in the graphene aerogel, and further affect the structure of the graphene aerogel.
The graphene aerogel prepared by the method does not contain other impurities which affect the conductivity, the obtained graphene aerogel has a high specific surface area and a large pore diameter, an aluminum coating layer is easy to form, the graphene aerogel also has a low density, the material can be lightened, and meanwhile, the graphene aerogel also has high conductivity.
In some embodiments, the graphene aerogel has a specific surface area of 100m2/g～400m2The pore diameter is 5nm to 15 nm. The specific surface area of the graphene aerogel can be independently selected to be 150m2/g、200m2/g、250m2/g、300m2/g、350m2/g。
In some embodiments, the graphene aerogel has a density of 50mg/cm3～150mg/cm3。
In some embodiments, the electrolytic salt may include one or more of sodium chloride, potassium chloride, and aluminum chloride. In a preferred embodiment, the electrolytic salts are sodium chloride, potassium chloride and aluminum chloride. The mass ratio of sodium chloride, potassium chloride and aluminum chloride may be 1: (1-3): (6-10), 1:2:6, 1:2:7, 1:2:8, 1:2:9, 1:3:7, 1:2:8, 1:2:9, 1:1:7, 1:1:8, 1:1:9 may also be selected.
In some embodiments, the temperature of the molten electrolytic salt is 180 ℃ to 220 ℃, and 190 ℃, 200 ℃ and 210 ℃ can be selected.
In one embodiment, the electrolytic salt may be previously dried.
The embodiment of the invention also provides the graphene-aluminum composite material prepared by the preparation method of the graphene-aluminum composite material.
The graphene-aluminum composite material comprises a graphene hydrogel matrix and an aluminum-plated layer formed on the matrix. The thickness of the aluminum-plated layer may be 50 μm to 1 mm.
Embodiments of the present invention further provide a cable or wire comprising the graphene aluminum composite material according to claim 9 or 10.
The following are specific examples:
example 1
(1) 10g of sodium chloride, 10g of potassium chloride and 80g of aluminum chloride were weighed and dried at 120 ℃ for 4 hours, respectively.
(2) 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.
(3) Will be provided withMixing the dried sodium chloride, potassium chloride and aluminum chloride in the step (1), putting the mixture into an electrolytic cell to be used as electrolytic salt, and simultaneously adding the mixture with the diameter of
And (3) taking the pure aluminum rod as an anode, taking the graphene aerogel prepared in the step (2) as a cathode, respectively inserting the graphene aerogel into electrolytic salt, then pumping the vacuum degree of the electrolytic cell to be below 5Pa through a vacuum pump, and then introducing argon to normal pressure.
(4) Heating the electrolytic bath to 200 deg.C, and maintaining the temperature to make the electrolytic salt melt.
(5) And (3) introducing 300mA electrolysis current into the electrolysis device, electrolyzing for 60min, taking out the cathode after electrolysis, and washing with deionized water to obtain the graphene-aluminum composite material.
Example 2
Substantially the same as in example 1 except that 60g of aluminum chloride was used in step (1).
Example 3
The same as in example 1 except that 100g of aluminum chloride was used in step (1).
Example 4
Substantially the same as in example 1 except that in step (5), the electrolytic current was 250 mA.
Example 5
Substantially the same as in example 1 except that in step (5), the electrolytic current was 350 mA.
Comparative example
And (3) immersing the graphene aerogel prepared in the step (2) in the embodiment 1 in molten aluminum for 40min, and then air-cooling to obtain the graphene aluminum composite material.
Test example
The graphene aluminum composite materials prepared in examples 1 to 5 and comparative example were subjected to tensile strength and conductivity tests. The tensile strength test is that the material is cut into a shape of a dog bone with a stretching interval of 18mm by a wire, after surface polishing, a universal experimental stretcher is used for tensile test, the stretching speed is 0.5mm/min, the conductivity test method is that after the surface of the material is mechanically polished, an eddy current conductivity meter is used for testing, and the test result is shown in table 1:
TABLE 1
| Tensile strength/MPa | Conductivity/% IACS | |
| Example 1 | 55 | 75 |
| Example 2 | 48 | 72 |
| Example 3 | 50 | 70 |
| Example 4 | 51 | 72 |
| Example 5 | 47 | 73 |
| Comparative example | 36 | 70 |
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, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The preparation method of the graphene-aluminum composite material is characterized by comprising the following steps:
providing graphene aerogel and placing the graphene aerogel serving as a cathode in molten electrolytic salt, wherein the anode is metal aluminum, the electrolytic current is 250-350 mA, the electrolytic salt is sodium chloride, potassium chloride and aluminum chloride, and the mass ratio of the sodium chloride to the potassium chloride to the aluminum chloride in the electrolytic salt is 1: (1-3): (6-10).
2. The preparation method of the graphene aluminum composite material according to claim 1, wherein the graphene aerogel is formed into the graphene aerogel by an ice template method.
3. The preparation method of the graphene aluminum composite material according to claim 2, wherein the method for forming the graphene aerogel by the ice template method comprises the following steps:
carrying out vacuum freeze drying on the graphene oxide aqueous solution, wherein the freeze drying temperature is-50 ℃ to-75 ℃, and the freeze drying time is 20h to 30 h; and
and (3) performing vacuum heat treatment reduction, wherein the heat treatment temperature is 1500-2500 ℃, and the heat treatment reduction time is 2-4 h.
4. The preparation method of the graphene-aluminum composite material according to any one of claims 1 to 3, wherein the density of the graphene aerogel is 50mg/cm3～150mg/cm3。
5. The preparation method of the graphene-aluminum composite material according to any one of claims 1 to 3, wherein the graphene aerogel has a pore diameter of 5nm to 15nm and a specific surface area of 100m2/g～400m2/g。
6. The preparation method of the graphene-aluminum composite material according to claim 1, wherein the mass ratio of sodium chloride, potassium chloride and aluminum chloride in the electrolytic salt is 1:1: 8.
7. A graphene-aluminum composite material prepared by the method for preparing a graphene-aluminum composite material according to any one of claims 1 to 6.
8. The graphene aluminum composite material according to claim 7, comprising a graphene aerogel substrate and an aluminum plated layer formed on the substrate, wherein the aluminum plated layer has a thickness of 50 μm to 1 mm.
9. A cable or wire comprising the graphene aluminum composite material according to claim 7 or 8.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649477A (en) * | 2009-09-11 | 2010-02-17 | 中国工程物理研究院激光聚变研究中心 | Preparation method of metal carbon aerogel composite material |
| CN104205445A (en) * | 2012-03-22 | 2014-12-10 | 住友电气工业株式会社 | Metal three-dimensional, mesh-like porous body for collectors, electrode, and non-aqueous electrolyte secondary battery |
| CN104694989A (en) * | 2015-03-12 | 2015-06-10 | 上海理工大学 | Preparation method of graphene-base metal composite material |
| WO2015087948A1 (en) * | 2013-12-12 | 2015-06-18 | 住友電気工業株式会社 | Carbon material-coated metal porous body, collector, electrode, and power storage device |
| CN105247084A (en) * | 2013-05-31 | 2016-01-13 | 住友电气工业株式会社 | Production method for porous aluminum body, porous aluminum body, current collector, electrode, and electrochemical device |
| CN109336093A (en) * | 2018-12-04 | 2019-02-15 | 上海交通大学 | A kind of preparation method of graphene aerogel |
| CN110536979A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of porous body of composite metal and porous body of composite metal |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649477A (en) * | 2009-09-11 | 2010-02-17 | 中国工程物理研究院激光聚变研究中心 | Preparation method of metal carbon aerogel composite material |
| CN104205445A (en) * | 2012-03-22 | 2014-12-10 | 住友电气工业株式会社 | Metal three-dimensional, mesh-like porous body for collectors, electrode, and non-aqueous electrolyte secondary battery |
| CN105247084A (en) * | 2013-05-31 | 2016-01-13 | 住友电气工业株式会社 | Production method for porous aluminum body, porous aluminum body, current collector, electrode, and electrochemical device |
| WO2015087948A1 (en) * | 2013-12-12 | 2015-06-18 | 住友電気工業株式会社 | Carbon material-coated metal porous body, collector, electrode, and power storage device |
| CN104694989A (en) * | 2015-03-12 | 2015-06-10 | 上海理工大学 | Preparation method of graphene-base metal composite material |
| CN110536979A (en) * | 2017-05-22 | 2019-12-03 | 住友电气工业株式会社 | The manufacturing method of porous body of composite metal and porous body of composite metal |
| CN109336093A (en) * | 2018-12-04 | 2019-02-15 | 上海交通大学 | A kind of preparation method of graphene aerogel |
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