阅读说明：本技术 金属包覆碳纳米管的制备方法 (Preparation method of metal-coated carbon nano tube ) 是由 王金娥 董明 于 2019-11-07 设计创作，主要内容包括：一种金属包覆碳纳米管的制备方法,属于纳米材料技术领域。该金属包覆碳纳米管的制备方法包括以下步骤：S1,将碳纳米管制备成大孔径大孔隙率的碳纳米管纸；S2,采用超高真空状态下蒸发或低真空下冷态溅射的工艺在碳纳米管管纸上包覆所述金属单质,得到在纳米尺度金属与碳纳米管比例可控且均匀复合的金属包覆碳纳米管纸。本发明提高了碳纳米管与金属基体的相亲性,适合大规模产业化生产。(A preparation method of a metal-coated carbon nanotube belongs to the technical field of nano materials. The preparation method of the metal-coated carbon nano tube comprises the following steps: s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity; and S2, coating the metal simple substance on the carbon nanotube paper by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition. The invention improves the affinity of the carbon nano tube and the metal matrix, and is suitable for large-scale industrial production.)

1. A preparation method of a metal-coated carbon nanotube is characterized by comprising the following steps:

s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity;

s2, coating the carbon nanotube paper with a metal simple substance by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition.

2. The method of claim 1, wherein in step S2, the evaporation under ultra-high vacuum or cold sputtering under low vacuum is selected according to the melting point of the metal to be coated.

3. The method of claim 1, wherein the thickness of the metal coated on the carbon nanotube paper is 5 to 100 nm.

4. The method of claim 1, wherein the carbon nanotubes are at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes, and have a diameter of 10 to 200nm and a length of 5 to 20 μm.

5. The method of claim 3, wherein the carbon nanotube paper has a thickness of 100 to 1000 μm.

6. The method of claim 1, wherein the method of preparing the carbon nanotube paper comprises the steps of:

s11, mixing the carbon nano tube, the surfactant and the mixed solution of the deionized water and the alcohol, and uniformly stirring and dispersing to obtain carbon nano tube slurry;

s12, uniformly coating the carbon nanotube slurry prepared in the step S11 on the surface of the rough copper foil, and drying at 70-80 ℃;

and S13, tearing off the carbon nanotube film dried in the step S12 and rolling the carbon nanotube film into a carbon nanotube paper roll to obtain the carbon nanotube paper with large aperture and large porosity.

7. The method for preparing the metal-coated carbon nanotube according to claim 6, wherein the ratio of the deionized water to the alcohol is 1 to 2: 1.

8. the method of claim 1, wherein the metal-coated carbon nanotube paper is used as a functional foil or crushed as functional powder.

Technical Field

The invention relates to a technology in the field of nano materials, in particular to a preparation method of a metal-coated carbon nano tube.

Background

Carbon nanotubes have achieved a certain level of performance as reinforcing phases in composite materials such as Fe-based, Al-based, Cu-based, Mg-based, and Ni-based materials. However, due to strong van der waals force between the carbon nanotubes, the carbon nanotubes are very easy to agglomerate, and thus the carbon nanotubes are difficult to be uniformly dispersed in the composite material. As long as the carbon nanotubes are uniformly dispersed in the metal matrix and form effective interface bonding with the metal matrix by adopting a proper method, the carbon nanotubes can be used as a reinforcing phase to obviously improve the performance of the metal matrix composite.

Coating a metal coating on the surface of the carbon nanotube is an effective means for solving the above problems. For example, in the article "platinum deposition on carbon nanotubes" (for example, nobility, record, Mao Zong et al. science bulletin, 1999, 44(11): 1154-1157), "surface modification and nickel coating of carbon nanotubes" (for the easy army, Xiaohua, Jiangxing et al. Chinese non-ferrous metals bulletin, 2004, 14(3): 479-483), "research on coating carbon nanotubes with Ni-Co alloy" (Chenxiaohua, Yangyong, Zhang Gaoming et al. microfabrication technology, 1999, 2: 17-22), "chemical silver plating and SEM research on carbon nanotubes" (Chenxiaohua, Zhang Gao Ming, Li Mao et al. Hunan university of south university, 1999, 26(6): 14-18), etc., the acid treatment → activation of metals Sn and Pt and → sensitization chemical codeposition of carbon nanotubes are used, although different metal coatings are successfully coated on the surface of carbon nanotubes, but the used process is complicated, the price is high, and the toxic reagent is not environment-friendly, is not suitable for large-scale production and is difficult to industrialize when being commonly used; the article In situ chemical vapor deposition of metal on metal-grown carbon fibers and contamination of aluminum-matrix compounds recycled by coated fibers (Fumio Ogawa et al J Mater Sci, 2018, 53: 5036-5050) adopts an In situ chemical vapor deposition method to heat metal powder and iodine In a quartz tube to generate metal iodide vapor, and then annealing and depositing the metal iodide vapor to successfully deposit aluminum, nickel, silicon and titanium on the surface of VGCFs, however, the method is not only complicated In process, but also the equipment system is more complicated and expensive, and is not suitable for large-scale production.

The present invention has been made to solve the above-mentioned problems occurring in the prior art.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a preparation method of the metal-coated carbon nano tube, which improves the affinity of the carbon nano tube and a metal matrix and is suitable for large-scale industrial production.

The invention comprises the following steps:

s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity;

s2, coating the carbon nanotube paper with a metal simple substance by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition.

In step S2, the evaporation process in the ultra-high vacuum state or the cold sputtering process in the low vacuum state is determined according to the melting point of the elemental metal to be coated.

Preferably, the thickness of the metal coating layer is 5-100 nm, and more preferably 20-50 nm.

Preferably, the carbon nanotube is at least one of a single-walled carbon nanotube and a multi-walled carbon nanotube, the diameter is 10-200 nm, and the length is 5-20 μm.

Preferably, the thickness of the carbon nanotube paper is 100-1000 μm, and more preferably 200-500 μm.

Preferably, the preparation method of the carbon nanotube paper comprises the following steps:

s11, mixing the carbon nano tube, the surfactant and the mixed solution of the deionized water and the alcohol, and uniformly stirring and dispersing to obtain carbon nano tube slurry;

s12, uniformly coating the carbon nanotube slurry prepared in the step S11 on the surface of the rough copper foil, and drying at 70-80 ℃;

and S13, tearing off the carbon nanotube film dried in the step S12 and rolling the carbon nanotube film into a carbon nanotube paper roll to obtain the carbon nanotube paper with large aperture and large porosity.

Preferably, the surfactant is a nonionic surfactant, and comprises at least one of PEG, PVP and PVA.

Preferably, the ratio of the deionized water to the alcohol is 1: 1-2.

Preferably, the metal-coated carbon nanotube paper can be used as a functional foil and also can be crushed to be used as functional powder; the pulverization method includes but is not limited to milling media type pulverization, ultramicro pulverization and air flow pulverization.

Technical effects

Compared with the prior art, the invention has the following technical effects:

1) the method is simple, efficient and environment-friendly, and can be used for producing the metal-coated carbon nanotube powder in a large scale to obtain the functional material with controllable M/C ratio and uniform composition of metal and carbon nanotubes in nano scale;

2) the nano metal layer uniformly coated on the surface of the carbon nano tube can effectively avoid the repulsion of metal crystal boundaries to the carbon nano tube, so that the carbon nano tube can easily enter metal when the metal-based composite material is prepared;

3) the method can greatly improve the affinity of the carbon nano tube and the metal matrix and can effectively solve the problem of uniform dispersion of the carbon nano tube in the metal matrix composite.

Drawings

FIG. 1 is an SEM photograph of a nano-silver coated carbon nanotube composite material prepared in example 1 of the present invention;

fig. 2 is an XRD spectrum of the nano-silver coated carbon nanotube composite material prepared in example 1 of the present invention.

Detailed Description

The invention is described in detail below with reference to the drawings and the detailed description.