阅读说明：本技术 一种碳纳米管与二氧化钛纳米片管状复合材料的制备方法 (Preparation method of carbon nanotube and titanium dioxide nanosheet tubular composite material ) 是由 姜克亮 王成 于 2019-11-27 设计创作，主要内容包括：本发明涉及到纳米复合材料领域,具体而言,涉及到一种碳纳米管与二氧化钛纳米片管状复合材料的制备,包括以下步骤：(1)称取一定量的碳纳米管放到烧杯中,加入N,N-二甲基甲酰胺和异丙醇,得到混合溶液；(2)将混合溶液在超声机中超声；往分散均匀的混合液中加入钛酸四丁酯,再超声；(3)将混合液转移到高压釜中封装好放到烘箱中,进行水热处理；(4)得到的产物用水和乙醇在离心机中进行离心处理,将离心后的产物放到烘箱中烘干,得到前驱体；(5)将产物转移到石英舟中,在管式炉中进行高温煅烧。本发明有益效果是：本发明通过调节碳纳米管和碳酸四丁酯的量,最终得到尺寸均匀的介孔的超薄二氧化钛纳米片管状材料,复合材料具有很高的结晶性且包含两种晶相,锐钛矿和板钛矿相,并且纳米片是由很小的纳米颗粒组成,颗粒与颗粒间形成的微小界面,增加了锂离子的嵌入位点,提高电池容量。(The invention relates to the field of nano composite materials, in particular to a preparation method of a carbon nano tube and titanium dioxide nano sheet tubular composite material, which comprises the following steps: (1) weighing a certain amount of carbon nanotubes, putting the carbon nanotubes into a beaker, and adding N, N-dimethylformamide and isopropanol to obtain a mixed solution; (2) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine; adding tetrabutyl titanate into the uniformly dispersed mixed solution, and then carrying out ultrasonic treatment; (3) transferring the mixed solution into a high-pressure kettle, packaging, putting into an oven, and carrying out hydrothermal treatment; (4) centrifuging the obtained product in a centrifuge by using water and ethanol, and drying the centrifuged product in an oven to obtain a precursor; (5) the product was transferred to a quartz boat and calcined at high temperature in a tube furnace. The invention has the beneficial effects that: according to the invention, the mesoporous ultrathin titanium dioxide nanosheet tubular material with uniform size is finally obtained by adjusting the amounts of the carbon nanotube and the tetrabutyl carbonate, the composite material has high crystallinity and comprises two crystal phases, namely anatase phase and brookite phase, and the nanosheet is composed of very small nanoparticles, and a tiny interface formed between the particles increases the intercalation sites of lithium ions and improves the battery capacity.)

1. The preparation method of the carbon nanotube and titanium dioxide nanosheet tubular composite material is characterized by comprising the following steps of: weighing a certain amount of carbon nanotubes as a base, putting the base in a beaker, adding N, N-dimethylformamide and isopropanol to obtain a mixed solution, and carrying out ultrasound treatment on the mixed solution in an ultrasonic machine; adding tetrabutyl titanate, and then carrying out ultrasonic treatment and dispersion. The mixed solution is transferred to an autoclave and put into an oven for hydrothermal treatment. The obtained product is centrifuged by water and ethanol in a centrifuge and then put into an oven for drying. And transferring the dried product into a quartz tube, and calcining the quartz tube in a tube furnace at a high temperature to obtain a black product.

2. The method for preparing the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material with uniform size according to claim 1, wherein the method comprises the following steps: 1-10mg of carbon nano tube and 50ml of beaker are taken, and then 1-20ml of N, N-dimethylformamide and 10-40ml of isopropanol are added to obtain a mixed solution.

3. The method for preparing the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material with uniform size according to claim 1, wherein the method comprises the following steps: and (3) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine for 30min, adding 1-5ml of tetrabutyl titanate, and carrying out ultrasonic treatment for 10 min.

4. The method for preparing the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material with uniform size according to claim 1, wherein the method comprises the following steps: the solution is transferred into an autoclave and then transferred into an oven, the temperature is set to be 100 ℃ and 300 ℃, and the growth time is 12-72 h.

5. The method for preparing the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material with uniform size according to claim 1, wherein the method comprises the following steps: after the reaction is finished, the reaction product is naturally cooled to room temperature, the obtained product is poured into a centrifuge tube, and then the centrifuge tube is centrifuged for three times by deionized water and ethanol respectively for SEM test.

6. The method for preparing the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material with uniform size according to claim 1, wherein the method comprises the following steps: and putting part of the product into a quartz tube to be calcined in a tube furnace, wherein the temperature is set to 350-800 ℃, and the calcination time is 1-6 h.

The technical field is as follows:

the invention relates to the field of nano composite materials, in particular to a preparation method of a carbon nano tube and titanium dioxide nano sheet tubular composite material.

Background of the invention:

titanium dioxide is a multifunctional application material, and has the advantages of excellent physical-chemical properties of stability, mild environment, low consumption and the like. Its commercial products can be found widely in paints, lacquers, coatings and sun blocks. In the early 70 s of the 20 th century, the research on photocatalytic hydrolysis by using titanium dioxide as an electrode became a research hotspot at that time, which makes titanium dioxide attract extensive attention in the fields of photocatalysis and energy sources. Due to the appropriate electronic band gap structure and excellent surface activity, the titanium dioxide has considerable application prospects in the fields of hydrogen production, photocatalysis, lithium ion batteries, fuel cells, supercapacitors, meteorological sensors and the like.

Indeed, the main applications of titanium dioxide are based on its nano-size, morphology, and especially nanoparticle morphology. In the nanometer size, the transport behavior of electrons and holes can be changed and the electronic band gap structure can be transferred due to the appearance of quantum confinement effect. This extremely large ratio of specific surface area to volume of the nanomaterial can significantly increase the surface reaction sites and modulate the catalytic activity of the surface atoms. Therefore, further improvements in the performance of titania-based materials and devices have mainly relied on the development of nanostructures that optimize their composite components, improve crystallinity and integrity.

The invention content is as follows:

aiming at the problems of the existing titanium dioxide nano composite material in practical application, the invention provides a preparation method of a carbon nano tube and ultrathin titanium dioxide nano sheet tubular composite material with uniform size. The purpose is to apply the carbon nano tube and titanium dioxide nano sheet tubular composite material to a lithium ion battery, improve the intercalation sites of lithium ions and further improve the battery capacity.

The technical scheme of the invention is as follows:

(1) taking a certain amount of carbon nanotubes and putting the carbon nanotubes into a beaker;

(2) adding N, N-dimethylformamide and isopropanol to obtain a mixed solution;

(3) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine;

(4) then adding tetrabutyl titanate into the uniformly dispersed mixed solution obtained in the step (3), and then carrying out ultrasonic treatment;

(5) transferring the mixed solution in the step (4) to a high-pressure kettle, putting the high-pressure kettle into an oven, and carrying out hydrothermal treatment;

(6) centrifuging the product obtained in the step (5) in a centrifuge by using water and ethanol;

(7) putting the product obtained after centrifugation in the step (6) into an oven for drying to obtain a precursor, and carrying out SEM test;

(8) and (5) transferring the precursor in the step (7) into a quartz tube, and carrying out high-temperature calcination in a tube furnace.

The invention has the following advantages:

(1) the preparation method is a hydrothermal method, is simple and efficient, is suitable for large-scale production, and uses polyacrylic acid as a surfactant to avoid large-scale agglomeration of particles so as to form a composite structure;

(2) the glacial acetic acid is utilized to acidify the solution, so that the environmental pollution is small.

Description of the drawings:

FIG. 1(a, b) is a scanning electron micrograph of a nanosheet tubular precursor in example 1;

FIG. 2(a, b) is the scanning electron micrograph of the nanosheet tubular precursor in example 2;

FIG. 3(a, b) is the scanning electron micrograph of the nanosheet tubular precursor in example 3;

FIG. 4(a, b, c) is a transmission electron micrograph of the nanosheet tubular precursor in example 3;

FIG. 5(a, b) is the scanning electron microscope image of the carbon nanotube and anatase phase titanium dioxide nanosheet tubular composite in example 3;

FIG. 6(a, b, c, d) is a transmission electron microscope image of the carbon nanotube and anatase phase titanium dioxide nanosheet tubular composite in example 3;

FIG. 7(a, b, c) is a high-resolution transmission electron microscope image of the tubular composite material of titanium dioxide nano-sheet with carbon nanotube and anatase crystalline phase, and (d, e, f, g) are the corresponding element distribution diagrams respectively;

fig. 8(a, b) are X-ray powder diffraction pattern and thermogravimetric analysis pattern of the titanium dioxide nanosheet tubular composite material with carbon nanotubes and anatase crystalline phase, respectively.

The specific implementation mode is as follows:

the present invention is further illustrated by the following examples, which are not limited to the following specific examples, and example 3 is an optimal preparation condition of the carbon nanotube and ultrathin titanium dioxide nanosheet tubular composite material.

Example 1:

(1) putting 10mg of carbon nano tube into a 50ml beaker, and then adding 5ml of N, N-dimethylformamide and 15ml of isopropanol to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine for 30min, adding 5ml of tetrabutyl titanate, and carrying out ultrasonic treatment for 5 min;

(3) transferring the solution into a 50ml high-pressure kettle, setting the temperature of an oven at 150 ℃ and the growth time at 20 h;

(4) and pouring the obtained product into a centrifuge tube, washing and centrifuging the product for multiple times by using deionized water and ethanol, transferring the product into an oven, drying the product, and performing SEM test.

Example 2:

(1) putting 8mg of carbon nano tube into a 50ml beaker, and then adding 5ml of N, N-dimethylformamide and 15ml of isopropanol to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine for 30min, adding 3ml of tetrabutyl titanate, and carrying out ultrasonic treatment for 5 min;

(3) transferring the solution into a 50ml high-pressure kettle, setting the temperature of an oven at 150 ℃ and the growth time at 20 h;

(4) and pouring the obtained product into a centrifuge tube, washing and centrifuging the product for multiple times by using deionized water and ethanol, transferring the product into an oven, drying the product, and performing SEM test.

Example 3:

(1) taking 5mg of carbon nano tube and a 50ml beaker, and then adding 5ml of N, N-dimethylformamide and 15ml of isopropanol to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution in an ultrasonic machine for 30min, adding 1ml of tetrabutyl titanate, and carrying out ultrasonic treatment for 5 min;

(3) transferring the solution into a 50ml high-pressure kettle, setting the temperature of an oven at 180 ℃, and setting the growth time to be 20 h;

(4) pouring the obtained product into a centrifuge tube, then washing and centrifuging the product for multiple times by using deionized water and ethanol, transferring the product into a drying oven, drying the product, and carrying out SEM test;

(5) and transferring the dried product into a quartz boat, and calcining the quartz boat in a tube furnace at high temperature of 500 ℃ for 4h to finally obtain a black product.

The above examples show that: the hydrothermal synthesis method provided by the invention provides a cheap and environment-friendly preparation method of the carbon nano tube and ultrathin titanium dioxide nano sheet tubular composite material with uniform size.