Method for preparing graphene through liquid metal vapor deposition
阅读说明：本技术 一种液态金属气相沉积制备石墨烯的方法 (Method for preparing graphene through liquid metal vapor deposition ) 是由 胡晶娟 于 2019-10-15 设计创作，主要内容包括：本发明公开了一种液态金属气相沉积制备石墨烯的方法,包括以下步骤：1)将基体铜、镍或铜镍合金清洗后,置于气相沉积炉的石墨坩埚中,通入氮气保持压力为0.1Mpa以上；2)升温加热熔融为铜、镍或铜镍熔融液；3)向熔融液中通入气态烷烃,石墨烯随气体飘浮至熔融液面上,4)停止通入气态烷烃后,停止加热,直到熔融液冷却凝固后停止通入氮气,所得产品经三氯化铁和盐酸混合溶液进行酸洗去除基体,清洗后干燥得石墨烯成品。本发明创造性的在熔融的液态金属中鼓泡生产石墨烯,实现高品质连续生产,大大提高生产效率。(The invention discloses a method for preparing graphene by liquid metal vapor deposition, which comprises the following steps: 1) cleaning a matrix of copper, nickel or copper-nickel alloy, placing the matrix in a graphite crucible of a vapor deposition furnace, and introducing nitrogen to keep the pressure above 0.1 MPa; 2) heating and melting the mixture into copper, nickel or copper-nickel molten liquid; 3) and (2) introducing gaseous alkane into the molten liquid, floating the graphene to the molten liquid surface along with the gas, 4) stopping introducing the gaseous alkane, stopping heating until the molten liquid is cooled and solidified, stopping introducing nitrogen, performing acid washing on the obtained product by using a mixed solution of ferric trichloride and hydrochloric acid to remove a matrix, and drying after cleaning to obtain a graphene finished product. The invention creatively produces the graphene by bubbling in the molten liquid metal, realizes high-quality continuous production and greatly improves the production efficiency.)
1. A method for preparing graphene by liquid metal vapor deposition is characterized by comprising the following steps:
1) cleaning a matrix of copper, nickel or copper-nickel alloy, placing the matrix in a graphite crucible of a vapor deposition furnace, vacuumizing the vapor deposition furnace, introducing nitrogen into the system to positive pressure, and repeatedly operating for three times until the nitrogen pressure of the system is kept above 0.1 MPa;
2) at 800 and 1200Nm3Velocity per hourIntroducing nitrogen, starting an electric heating system, heating and melting copper, nickel or copper-nickel alloy into copper, nickel or copper-nickel molten liquid, and heating to 1100-1500 ℃;
3) adding molten liquid at a ratio of 20-100Nm3Introducing gaseous alkane, wherein the graphene floats to the molten liquid level along with the gas, and the volume of the introduced gaseous alkane per hour is 200-300% of the volume of the molten liquid;
4) stopping heating after the gas alkane is stopped, stopping introducing nitrogen after the molten liquid is cooled and solidified, carrying out acid washing on the obtained product by using a mixed solution of ferric trichloride and hydrochloric acid to remove a matrix, cleaning, and drying to obtain a graphene finished product.
2. The method for preparing graphene according to claim 1, wherein the gaseous alkane is natural gas, methane, acetylene or propane.
3. The method for preparing graphene according to claim 1, wherein in the step 1), the substrate of copper, nickel or copper-nickel alloy is sequentially cleaned by acetone and deionized water.
4. The method for preparing graphene by liquid metal vapor deposition according to claim 1, wherein the vapor deposition furnace is cooled by circulating water.
5. The method for preparing graphene by vapor deposition of liquid metal according to claim 1, wherein a plurality of gas inlets are distributed at the bottom of a graphite crucible of the vapor deposition furnace, and the gaseous alkane is introduced into the copper liquid in a bottom gas inlet mode.
6. The method for preparing graphene according to claim 1, wherein a gas distributor is arranged in a graphite crucible of the vapor deposition furnace, and the gaseous alkane is introduced into the copper liquid through the gas distributor.
7. The method for preparing graphene through liquid metal vapor deposition according to claim 1, wherein the mass ratio of ferric trichloride to hydrochloric acid in the mixed solution of ferric trichloride and hydrochloric acid is 3: 1.
Technical Field
The invention relates to a method for preparing graphene by liquid metal vapor deposition.
Background
The CVD vapor deposition method is the best method for producing high-quality graphene at present, carbon-containing gas is introduced to a high-temperature copper foil in a closed environment, carbon atoms are decomposed at high temperature and orderly arranged on the surface of the copper foil to generate graphene, and the produced graphene is high in quality, but has the defects of low efficiency, high cost, incapability of large-scale production and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the defects of the prior art, provides a method for preparing graphene by liquid metal vapor deposition, creatively produces graphene by bubbling in molten liquid metal, realizes high-quality continuous production, and greatly improves the production efficiency.
The technical scheme is as follows: the method for preparing graphene by liquid metal vapor deposition comprises the following steps:
1) cleaning a matrix of copper, nickel or copper-nickel alloy, placing the matrix in a graphite crucible of a vapor deposition furnace, vacuumizing the vapor deposition furnace, introducing nitrogen into the system to positive pressure, and repeatedly operating for three times until the nitrogen pressure of the system is kept above 0.1 MPa;
2) at 800 and 1200Nm3Introducing nitrogen at the speed of/h, starting an electric heating system, heating and melting copper, nickel or copper-nickel alloy into copper, nickel or copper-nickel molten liquid, and heating to 1100-;
3) adding molten liquid at a ratio of 20-100Nm3Introducing gaseous alkane, wherein the graphene floats to the molten liquid level along with the gas, and the volume of the introduced gaseous alkane per hour is 200-300% of the volume of the molten liquid;
4) stopping heating after the gas alkane is stopped, stopping introducing nitrogen after the molten liquid is cooled and solidified, carrying out acid washing on the obtained product by using a mixed solution of ferric trichloride and hydrochloric acid to remove a matrix, cleaning, and drying to obtain a graphene finished product.
Preferably, the gaseous alkane is natural gas, methane, acetylene or propane.
Preferably, the substrate copper, nickel or copper-nickel alloy is sequentially cleaned by acetone and deionized water.
Preferably, the vapor deposition furnace is cooled with circulating water.
Preferably, a plurality of gas inlets are distributed at the bottom of the graphite crucible of the vapor deposition furnace, and the gaseous alkane is introduced into the copper liquid in a bottom gas inlet mode, or a gas distributor is arranged in the graphite crucible of the vapor deposition furnace, and the gaseous alkane is introduced into the copper liquid through the gas distributor.
Has the advantages that:
1. the liquid metal vapor deposition method creatively uses molten liquid metal to replace solid metal, carbon-containing gas is introduced into the molten liquid metal, carbon cracking deposition and ordered arrangement are carried out on the surface of bubbles to generate graphene, the produced graphene floats on the surface of the liquid metal, and is continuously extracted through airflow, so that continuous production is realized.
2. Compared with the traditional vapor deposition method, the production efficiency of the product is very high; compared with a graphite oxide reduction method, the graphene product has a few defects and higher quality.
Drawings
Fig. 1 is an electron microscope scanning spectrum of a graphene product;
FIG. 2 is a Raman spectrum analysis chart of a graphene product;
fig. 3 is an atomic force microscope scanning spectrum of a graphene product.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.