阅读说明：本技术 一种织构化碳纤维布/碳纳米管复合材料的制备方法 (Preparation method of textured carbon fiber cloth/carbon nanotube composite material ) 是由 雷志斌 牛斐 张文亮 郭瑞 孙惠 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种织构化碳纤维布/碳纳米管复合材料的制备方法,该方法以浸渍了硝酸镍的棉布作为基底,硝酸镍作为镍源,乙腈作为碳源,在氮气气氛中碳化后化学气相沉积,通过调整硝酸镍的量、化学气相沉积时间以及氮气气流速度来控制碳纳米管的形貌。碳纳米管的生长不仅提高了织构化碳纤维布的导电性和力学性能,同时硝酸镍在被还原过程中在织构化碳纤维布上留下了丰富的孔道,增大了电极的比表面积,使得其作为超级电容器的电极,具有优异的电容特性。碳纳米管的相互交织有利于离子的传输,拓宽了该材料在储能领域的广泛应用；而且本发明原料易得,成本低廉,工艺简单,可以实现大规模生产。(The invention discloses a preparation method of a textured carbon fiber cloth/carbon nanotube composite material, which takes cotton cloth impregnated with nickel nitrate as a substrate, nickel nitrate as a nickel source and acetonitrile as a carbon source, and controls the morphology of a carbon nanotube by regulating the amount of the nickel nitrate, the chemical vapor deposition time and the flow velocity of nitrogen after carbonization in a nitrogen atmosphere and chemical vapor deposition. The growth of the carbon nano tube not only improves the conductivity and the mechanical property of the textured carbon fiber cloth, but also leaves rich pore channels on the textured carbon fiber cloth in the reduction process of the nickel nitrate, and increases the specific surface area of the electrode, so that the nickel nitrate serving as the electrode of the super capacitor has excellent capacitance characteristics. The mutual interweaving of the carbon nano tubes is beneficial to the transmission of ions, and the wide application of the material in the field of energy storage is widened; in addition, the invention has the advantages of easily available raw materials, low cost and simple process, and can realize large-scale production.)

1. A preparation method of a textured carbon fiber cloth/carbon nanotube composite material is characterized by comprising the following steps:

(1) ultrasonic cleaning waste cotton fiber fabrics in acetone, ethanol and deionized water in sequence, removing dust, impurities and organic pollutants on the surfaces of the fibers, and drying; soaking the cleaned and dried cotton fiber fabric in nickel nitrate water solution, drying the soaked cotton fiber fabric until the surface of the cotton fiber fabric is in a wet state without flowing water, and freeze-drying the cotton fiber fabric;

(2) heating the freeze-dried cotton fiber fabric to 700-900 ℃ under the protection of nitrogen, and carbonizing at the constant temperature for 60-90 minutes to obtain porous carbon fiber cloth loaded with nickel particles;

(3) and continuously keeping the temperature of 700-900 ℃ for 10-20 min under the nitrogen atmosphere, and introducing acetonitrile through nitrogen in the constant temperature process to grow the carbon nano tubes on the porous carbon fiber cloth in situ to obtain the textured carbon fiber cloth/carbon nano tube composite material.

2. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 1, wherein the method comprises the following steps: in the step (1), the concentration of the nickel nitrate in the nickel nitrate aqueous solution is 0.02-0.1 mol/L.

3. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 2, wherein the method comprises the following steps: in the step (1), the concentration of the nickel nitrate in the nickel nitrate aqueous solution is 0.05-0.06 mol/L.

4. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 2 or 3, wherein: in the step (1), the cleaned and dried cotton fiber fabric is soaked in a nickel nitrate water solution for 18-24 hours.

5. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 1, wherein the method comprises the following steps: in the step (1), drying at 50-80 ℃ after impregnation until the surface is in a wet state without flowing water.

6. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 1, wherein the method comprises the following steps: in the step (2), the temperature of the cotton fiber fabric after freeze drying is raised to 780-820 ℃ under the protection of nitrogen with the air flow rate of 20-35 sccm, and the cotton fiber fabric is carbonized at the constant temperature for 60-90 min to obtain the porous carbon fiber fabric loaded with nickel particles.

7. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 1 or 6, wherein: in the step (2), the temperature rise rate is 5-10 ℃/min.

8. The method for preparing the textured carbon fiber cloth/carbon nanotube composite material according to claim 6, wherein: and (3) continuously keeping the temperature of 780-820 ℃ for 12-15 min in a nitrogen atmosphere with the gas speed of 10-16 sccm, and introducing nitrogen into acetonitrile in the constant temperature process to grow the carbon nano tubes on the porous carbon fiber cloth in situ.

Technical Field

The invention belongs to the technical field of supercapacitors, and particularly relates to a preparation method of a textured carbon fiber cloth/carbon nanotube composite material.

Background

The textured carbon fiber cloth has a hollow structure and can be used as a growth substrate of an electrode material. Or directly applied to the supercapacitor in the form of an electrode. Lei topic group (Journal of Colloid and Interface science.553(2019)705-712) carbonizes cotton cloth as raw material to obtain textured carbon fiber cloth (TC), and then obtains a textured carbon fiber cloth (aTC) electrode with large specific surface area by activating potassium hydroxide to be applied to a super capacitor. Although the textured carbon fiber cloth has good application prospect as a supercapacitor electrode, the conductivity and the lower specific capacity limit the application of the textured carbon fiber cloth.

Carbon Nanotubes (CNTs), also known as buckytubes, are a quantum material with a particular structure (radial dimension is of the order of nanometers, axial dimension is of the order of micrometers, both ends of the tube are substantially sealed). Has excellent electrical conductivity, mechanical property and thermal conductivity. The flexible material is loaded on the flexible material, so that the conductivity, the mechanical property and the electrode loading capacity of the flexible material can be improved, and the performances of the electrode and a device are improved, which is paid attention to people. The Liu subject group (Energy storage Mater.11(2018)75-82) loads the material on flexible commercial carbon cloth, and an asymmetric super capacitor is assembled by taking the flexible commercial carbon cloth as an electrode. However, the commercial carbon cloth has high cost, complex process and tedious process, and thus the load of the carbon nanotubes on the flexible material and the application of the carbon nanotubes are limited.

Disclosure of Invention

The invention aims to overcome the defects of the two prior arts and provide a method for preparing a textured carbon fiber cloth/carbon nanotube composite material by growing helical carbon nanotubes on the textured carbon fiber cloth.

Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:

1. ultrasonic cleaning waste cotton fiber fabrics in acetone, ethanol and deionized water in sequence, removing dust, impurities and organic pollutants on the surfaces of the fibers, and drying; the cotton fiber fabric after being cleaned and dried is soaked in nickel nitrate water solution, and then is dried to a wet state without flowing water on the surface, and then is frozen and dried.

2. And heating the freeze-dried cotton fiber fabric to 700-900 ℃ under the protection of nitrogen, and carbonizing at the constant temperature for 60-90 minutes to obtain the porous carbon fiber cloth loaded with nickel particles.

3. And continuously keeping the temperature of 700-900 ℃ for 10-20 min under the nitrogen atmosphere, and introducing acetonitrile through nitrogen in the constant temperature process to grow the carbon nano tubes on the porous carbon fiber cloth in situ to obtain the textured carbon fiber cloth/carbon nano tube composite material.

In the step 1, the concentration of the nickel nitrate in the nickel nitrate aqueous solution is 0.02-0.1 mol/L, and preferably the concentration of the nickel nitrate is 0.05-0.06 mol/L.

In the step 1, preferably, the cotton fiber fabric after being cleaned and dried is soaked in nickel nitrate water solution for 18-24 h, and then dried at 50-80 ℃ until the surface is in a wet state without flowing water.

In the step 2, preferably, the temperature of the cotton fiber fabric after freeze drying is raised to 780-820 ℃ under the protection of nitrogen with the gas flow rate of 20-35 sccm, and the cotton fiber fabric is carbonized at the constant temperature for 60-90 min to obtain the porous carbon fiber fabric loaded with nickel particles.

In the step 2, the temperature rise rate is 5-10 ℃/min.

In the step 3, preferably, the temperature is kept constant at 780-820 ℃ for 12-15 min under the nitrogen atmosphere with the gas flow rate of 10-16 sccm, and acetonitrile is brought in through nitrogen in the constant temperature process, so that the carbon nano tubes grow on the porous carbon fiber cloth in situ.

The invention has the following beneficial effects:

1. the invention takes the waste cotton fiber fabric which is common in nature as the initial raw material, and obtains the textured carbon fiber fabric/carbon nanotube composite material by methods such as carbonization, chemical vapor deposition and the like. The raw material source is rich and cheap; the waste cotton fiber fabric belongs to waste articles, effectively recovers the waste articles, reduces the production cost of the spiral carbon nano tube, and realizes macro preparation.

2. Compared with the prior art, the method for preparing the carbon nano tube has the advantages of low production condition, simple process, short production period, easy control and capability of massively preparing the carbon nano tube with uniform appearance and height. The method realizes carbonization of the cotton fiber cloth in one step based on the cotton fiber cloth and realizes the load of the carbon nano tube on the textured carbon fiber cloth by using a CVD method; and the formation of the catalyst nickel leaves abundant holes on the textured carbon fiber cloth and replaces the high cost of the flexible substrate in the past process.

3. The textured carbon fiber cloth/carbon nanotube composite material prepared by the invention is used as a supercapacitor electrode material, the composite material not only can provide sufficient space for introducing other nano materials, but also the elastic interweaving network of the carbon nanotubes is beneficial to the transmission of electrolyte ions, and the application of the composite material in the field of energy storage is widened.

Drawings

Fig. 1 is a scanning electron micrograph of the textured carbon fiber cloth/carbon nanotube composite obtained in example 1.

Fig. 2 is an X-ray diffraction pattern of the textured carbon fiber cloth/carbon nanotube composite obtained in example 1.

FIG. 3 shows N of the textured carbon fiber cloth/carbon nanotube composite obtained in example 1₂Adsorption and desorption curves.

Fig. 4 is a cyclic voltammetry curve of the textured carbon fiber cloth/carbon nanotube composite material obtained in example 1 as a supercapacitor electrode at a high scanning speed in a 6.0M KOH aqueous solution.

Fig. 5 is a graph of rate capability of the textured carbon fiber cloth/carbon nanotube composite obtained in example 1.

Fig. 6 is a resistance curve of the textured carbon fiber cloth/carbon nanotube composite material obtained in example 1 under different bending angles.

Fig. 7 is a resistance curve of the textured carbon fiber cloth/carbon nanotube composite material obtained in example 1 during 1000 times of bending.

Fig. 8 is a scanning electron micrograph of the textured carbon fiber cloth/carbon nanotube composite obtained in example 2.

Fig. 9 is a scanning electron micrograph of the textured carbon fiber cloth/carbon nanotube composite obtained in example 3.

Fig. 10 is a scanning electron micrograph of the textured carbon fiber cloth/carbon nanotube composite obtained in example 4.

Detailed Description

The invention will be further explained in more detail below with reference to the drawings and examples, but the scope of protection of the invention is not limited to these examples.