Preparation method and application of carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode

Abstract

The invention provides a preparation method of a carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode. The method comprises the following steps: firstly, preparing porous foam graphene, and introducing a sulfonic acid group through chemical crosslinking and reduction treatment of graphene oxide to improve the hydrophilicity and electrochemical activity of the porous foam graphene; secondly, amino-modified carbon nanotubes are prepared through ammonia water treatment and surface modification, and the dispersity and binding capacity of the amino-modified carbon nanotubes are enhanced; and finally, alternately spraying the porous foam graphene and carbon nanotube grafted polyaniline (PANI) on a carbon cloth substrate to form the multi-layer conductive network composite electrode. According to the composite electrode, through the synergistic effect of the three materials, the high conductivity of graphene, the mechanical enhancement property of the carbon nanotubes and the high specific capacitance characteristic of polyaniline are combined, and efficient ion transmission and energy storage performance are achieved. The prepared composite electrode has high porosity, large specific surface area, excellent conductivity and stable electrochemical performance.

Description

Technical Field

[0001] The invention relates to a method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode, and belongs to the field of functional polymer materials and electrochemistry. Background Art

[0002] With the rapid development of modern electronic devices, the demand for flexible energy storage devices (such as supercapacitors) in portable electronic products, wearable devices and energy storage systems is gradually increasing. As an efficient energy storage device, supercapacitors have the characteristics of high power density, fast charging and discharging capabilities and good cycle life. However, to achieve its large-scale application, the performance of electrode materials needs to be further improved, including high specific capacitance, high conductivity, excellent mechanical flexibility and stability for long-term use.

[0003] At present, commonly used supercapacitor electrode materials include carbon-based materials, conductive polymers and oxide materials. Carbon-based materials (such as graphene and carbon nanotubes) have a large specific surface area and excellent conductivity, but their electrochemical activity is low, resulting in limited specific capacitance; while conductive polymers (such as polyaniline) can significantly improve energy storage performance due to their high pseudocapacitance characteristics, but are limited in practical applications due to their poor mechanical properties and limited cycle stability. Therefore, combining the advantages of different materials to design composite electrode materials has become an important research direction to solve this problem.

[0004] Graphene is one of the ideal composite material substrates due to its high conductivity, good chemical stability and two-dimensional structure. The specific surface area and ion transfer efficiency can be further improved by introducing porous foamed graphene. Carbon nanotubes can be used as supporting materials to improve the conductivity and flexibility of composite electrodes due to their high conductivity and good mechanical properties. In addition, polyaniline, as a typical conductive polymer, has attracted much attention due to its high pseudocapacitance properties. However, in practical applications, high-quality composite materials need to be prepared by reasonable methods to achieve uniformly distributed structures and stable electrochemical properties. Summary of the invention The object of the present invention is to provide a preparation method of a carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode and its use, so as to solve the above problems existing in the prior art.

[0006] The present invention is achieved through the following technical solutions: A method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode comprises the following steps: preparing porous foam graphene; The porous foamed graphene is dispersed in deionized water, sulfanilic acid, sodium nitrite and deionized water are added, and reacted in an ice water bath for 1 to 3 hours, and then concentrated sulfuric acid is added and reacted at 50 to 80° C. to obtain sulfonated porous foamed graphene; Preparation of surface-modified amino-modified carbon nanotubes; The surface-modified amino-modified carbon nanotubes, isopropanol, distilled water, hydrochloric acid, aniline and ammonium persulfate are mixed and reacted to obtain carbon nanotube-grafted polyaniline; The carbon nanotube grafted polyaniline is dispersed in distilled water to obtain a spray liquid A, the sulfonated porous foamed graphene is dispersed in water to obtain a spray liquid B, the spray liquid A and the spray liquid B are alternately sprayed on a single side surface of the carbon cloth to form a graphene layer and a carbon nanotube grafted polyaniline layer that are repeatedly alternately stacked, and the spraying of one graphene layer and one carbon nanotube grafted polyaniline layer is counted as one cycle, and the cycle is repeated multiple times, and after each cycle, the carbon cloth is frozen with liquid nitrogen, and then placed in an ice bath for 2 to 4 hours, and then repeatedly washed with deionized water and freeze-dried at -50°C to obtain a carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode.

[0007] As a preferred embodiment, the preparation method of the porous foam graphene is: The pH value of the graphene oxide dispersion is adjusted to 4-5, and a glutaraldehyde aqueous solution is added, mixed and reacted at 50-70° C. to obtain a three-dimensional porous graphene oxide foam; The three-dimensional porous graphene oxide foam is immersed in a hydrazine hydrate aqueous solution, reacted at 80-100° C., and then washed with deionized water until neutral to obtain porous foamed graphene.

[0008] As a preferred embodiment, the mass concentration of the glutaraldehyde aqueous solution is 20-30%, and the mass ratio of hydrazine hydrate to water in the hydrazine hydrate aqueous solution is 1:(20-25).

[0009] As a preferred embodiment, the mass ratio of the porous foam graphene to sulfanilic acid is (1-3): (15-20).

[0010] As a preferred embodiment, the preparation method of the surface-modified amino-modified carbon nanotubes is: The carbon nanotubes are dispersed in concentrated ammonia water and subjected to hydrothermal reaction at 90-100°C to obtain amino-modified carbon nanotubes; The amino-modified carbon nanotubes and tetrabutylammonium hydroxide, N, N -dimethylformamide and placed at room temperature for 24 h to obtain surface-modified amino-modified carbon nanotubes.

[0011] As a preferred embodiment, the mass ratio of the amino-modified carbon nanotubes to tetrabutylammonium hydroxide is (1-2):(3-6).

[0012] As a preferred embodiment, the mass ratio of carbon nanotubes to aniline in step S3 is (1-2): (4-7).

[0013] A use of the carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode obtained by the above-mentioned preparation method as a flexible electrode material in a supercapacitor.

[0014] The basic implementation principle of the present invention is: 1. First, graphene oxide is reacted with glutaraldehyde to form a three-dimensional network structure, and then the GO hydrogel is freeze-dried to obtain a three-dimensional porous graphene oxide foam. The graphene oxide foam is reduced with hydrazine hydrate to obtain a three-dimensional porous foam graphene. Finally, the porous foam graphene is reacted with sulfanilic acid to obtain a sulfonated porous foam graphene.

[0015] 2. First, the carbon nanotubes are modified with concentrated ammonia water to obtain amino-modified carbon nanotubes, and then modified with tetrabutylammonium hydroxide to obtain surface-modified amino-modified carbon nanotubes.

[0016] 3. The porous foam graphene and carbon nanotube grafted polyaniline are alternately coated on the carbon cloth by multi-layer alternating spraying to obtain a carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode material.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. Sulfonic acid groups (-SO3H) are introduced on the graphene surface through azotization reaction to improve hydrophilicity and electrochemical activity, while enhancing the binding ability with polyaniline.

[0018] 2. Through amino groups and surface modification, the chemical bonding ability of graphene with other components is increased, and the dispersibility and stability of the material are improved.

[0019] 3. Graphene, carbon nanotubes and polyaniline form a stable multi-level conductive network. Graphene and carbon nanotubes provide fast electron channels, while polyaniline provides high-capacitance energy storage capacity. The three synergistically improve the comprehensive performance of the composite electrode. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Other features, objects and advantages of the present invention will become more apparent from the detailed description of non-limiting embodiments made with reference to the following drawings: Figure 1 This is a structural diagram of the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode of the present invention; In the figure: 1, carbon cloth layer, 2, graphene layer, 3, carbon nanotube grafted polyaniline layer. DETAILED DESCRIPTION

[0021] The present invention is described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that, for those of ordinary skill in the art, several variations and improvements may be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.

[0022] Unless otherwise specified, all raw materials used in the present invention are commercially available.

[0023] Example 1 This embodiment provides a method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode, which specifically includes the following steps: 1) Preparation of porous graphene foam Take 50 mL of 1 mg / mL graphene oxide (GO) dispersion in a beaker, stir with a magnetic stirrer for 30 min, and adjust the pH value of the solution to 4. Measure 10 mL of glutaraldehyde solution (mass concentration 25%) and slowly add it to the GO solution while stirring. Continue stirring at room temperature for 2 h to form a preliminary three-dimensional network structure. Heat in a water bath at 60°C for 6 h. Cool naturally to room temperature. Take out the cross-linked GO hydrogel and wash it with deionized water three times to remove unreacted glutaraldehyde and other residues. Put the hydrogel in a freeze dryer and freeze-dry for 24 h to obtain a lightweight three-dimensional porous graphene oxide foam. Soak the dried graphene oxide foam in a hydrazine hydrate solution (mass ratio, hydrazine hydrate: water = 1:20). Heat in a constant temperature water bath at 90°C for 6 h. After the reaction is completed, wash the foam with a large amount of deionized water until the pH is close to neutral. The product is washed and vacuum dried to obtain a three-dimensional porous foam graphene.

[0024] 0.1 g of porous foam graphene dispersion was added to 100 mL of deionized water, and 1.5 g of sulfanilic acid, 0.5 g of sodium nitrite and 250 mL of deionized water were added, and the mixture was reacted in an ice-water bath for 2 h. 15 g of concentrated sulfuric acid was added, and the mixture was reacted at 70 °C for 12 h. The product was collected by centrifugation, washed with deionized water, and freeze-dried to obtain sulfonated porous foam graphene.

[0025] 2) Preparation of amino-modified carbon nanotubes 0.5 g of carbon nanotubes were added to the reactor, and then concentrated ammonia was added to the reactor. The reaction was carried out at 95 °C for 6 h. The amino-modified carbon nanotubes were obtained by filtration, washing and drying. 0.4 g of amino-modified carbon nanotubes, 2 g of tetrabutylammonium hydroxide and 50 g of N, N-dimethylformamide, and placed at room temperature for 24 h to allow tetrabutylammonium hydroxide to be fully loaded on the amino-modified carbon nanotubes to obtain surface-modified amino-modified carbon nanotubes.

[0026] 3) Preparation of carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode 0.05 g of surface-modified amino-modified carbon nanotubes, 0.5 g of isopropanol and 3 g of distilled water, 8 g of 2 mol / L hydrochloric acid solution, 0.1 g of aniline and 1 g of 10% ammonium persulfate aqueous solution were placed in a spray bottle to form spray liquid A. 20 mL of 1 mg / mL sulfonated porous foam graphene dispersion was placed in another spray bottle to form spray liquid B.

[0027] Spraying liquid A and spraying liquid B were alternately sprayed on a single side surface of a carbon cloth (size 2 cm×2 cm) to form repeatedly alternately stacked graphene layers and carbon nanotube-grafted polyaniline layers, and spraying one layer of graphene layer and one layer of carbon nanotube-grafted polyaniline layer was counted as one cycle. The cycle was repeated 5 times, and after each cycle, the carbon cloth was frozen with liquid nitrogen, then placed in an ice bath for 3 hours, and then repeatedly washed with deionized water and freeze-dried to obtain a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode.

[0028] The structure of the carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode prepared in Example 1 is as follows: Figure 1 As shown, it includes a carbon cloth layer 1, a graphene layer 2 and a carbon nanotube grafted polyaniline layer 3, wherein the graphene layer 2 and the carbon nanotube grafted polyaniline layer 3 are repeatedly and alternately arranged on a single side surface of the carbon cloth layer 1. The porosity of the composite electrode is 93.12%, and the specific surface area is 32.12 m 2 / g, the conductivity is 1.77 S / m. The specific capacitance of the composite electrode material is 189F / g under the condition of current density of 1 A / g.

[0029] Example 2 This embodiment provides a method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode, which specifically includes the following steps: 1) Preparation of porous graphene foam Take 50 mL of 1.5 mg / mL graphene oxide (GO) dispersion in a beaker, stir with a magnetic stirrer for 30 min, and adjust the pH value of the solution to 4.5. Measure 10 mL of glutaraldehyde solution (mass concentration 22%) and slowly add it to the GO solution while stirring. Continue stirring at room temperature for 2 h to form a preliminary three-dimensional network structure. Heat in a water bath at 60℃ for 6 h. Cool naturally to room temperature. Take out the cross-linked GO hydrogel and wash it with deionized water three times to remove unreacted glutaraldehyde and other residues. Put the hydrogel in a freeze dryer and freeze-dry for 24 h to obtain a lightweight three-dimensional porous graphene oxide foam. Soak the dried graphene oxide foam in a hydrazine hydrate solution (mass ratio, hydrazine hydrate: water = 1:20). Heat in a constant temperature water bath at 90℃ for 6 h. After the reaction is completed, wash the foam with a large amount of deionized water until the pH is close to neutral. The product is washed and vacuum dried to obtain a three-dimensional porous foam graphene.

[0030] 0.15 g of porous foam graphene dispersion was added to 100 mL of deionized water, and 2.0 g of sulfanilic acid, 0.5 g of sodium nitrite and 250 mL of deionized water were added, and the mixture was reacted in an ice-water bath for 2 h. 15 g of concentrated sulfuric acid was added, and the mixture was reacted at 70 °C for 12 h. The product was collected by centrifugation, washed with deionized water, and freeze-dried to obtain sulfonated porous foam graphene.

[0031] 2) Preparation of amino-modified carbon nanotubes 0.5 g of carbon nanotubes were added to the reactor, and then concentrated ammonia was added to the reactor. The reaction was carried out at 95 °C for 6 h, and then the amino-modified carbon nanotubes were obtained by filtration, washing and drying. N, N -dimethylformamide, and placed at room temperature for 24 h to allow tetrabutylammonium hydroxide to be fully loaded on the amino-modified carbon nanotubes to obtain surface-modified amino-modified carbon nanotubes.

[0032] 3) Preparation of carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode 0.04 g of surface-modified amino-modified carbon nanotubes, 0.5 g of isopropanol and 3 g of distilled water, 8 g of 2 mol / L hydrochloric acid solution, 0.09 g of aniline and 1 g of 10% ammonium persulfate aqueous solution were placed in a spray bottle to form spray liquid A. 20 mL of 1 mg / mL sulfonated porous foam graphene dispersion was placed in another spray bottle to form spray liquid B.

[0033] Spraying liquid A and spraying liquid B were alternately sprayed on a single side surface of a carbon cloth (size 2 cm×2 cm) to form repeatedly alternately stacked graphene layers and carbon nanotube-grafted polyaniline layers, and spraying one layer of graphene layer and one layer of carbon nanotube-grafted polyaniline layer was counted as one cycle. The cycle was repeated 5 times, and after each cycle, the carbon cloth was frozen with liquid nitrogen, then placed in an ice bath for 3 hours, and then repeatedly washed with deionized water and freeze-dried to obtain a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode.

[0034] The porosity of the composite electrode prepared in Example 2 is 94.15%, and the specific surface area is 33.99 m 2 / g, the conductivity is 1.82 S / m. The prepared composite electrode material has a specific capacitance of 179 F / g at a current density of 1 A / g.

[0035] Example 3 This embodiment provides a method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode, which specifically includes the following steps: 1) Preparation of porous graphene foam Take 50 mL of 1.5 mg / mL graphene oxide (GO) dispersion in a beaker, stir with a magnetic stirrer for 30 min, and adjust the pH value of the solution to 5. Measure 10 mL of glutaraldehyde solution (mass concentration 24%) and slowly add it to the GO solution while stirring. Continue stirring at room temperature for 2 h to form a preliminary three-dimensional network structure. Heat in a water bath at 60°C for 6 h. Cool naturally to room temperature. Take out the cross-linked GO hydrogel and wash it with deionized water three times to remove unreacted glutaraldehyde and other residues. Put the hydrogel in a freeze dryer and freeze-dry for 24 h to obtain a lightweight three-dimensional porous graphene oxide foam. Soak the dried graphene oxide foam in a hydrazine hydrate solution (mass ratio, hydrazine hydrate: water = 1:25). Heat in a constant temperature water bath at 90°C for 6 h. After the reaction is completed, wash the foam with a large amount of deionized water until the pH is close to neutral. The product is washed and vacuum dried to obtain a three-dimensional porous foam graphene.

[0036] 0.15 g of porous foam graphene dispersion was added to 100 mL of deionized water, and 1.7 g of sulfanilic acid, 0.5 g of sodium nitrite and 250 mL of deionized water were added, and the mixture was reacted in an ice-water bath for 2 h. 15 g of concentrated sulfuric acid was added, and the mixture was reacted at 70 °C for 12 h. The product was collected by centrifugation, washed with deionized water, and freeze-dried to obtain sulfonated porous foam graphene.

[0037] 2) Preparation of amino-modified carbon nanotubes 0.4 g of carbon nanotubes were added to the reactor, and then concentrated ammonia was added to the reactor. The reaction was carried out at 95 °C for 6 h, and then the amino-modified carbon nanotubes were obtained by filtration, washing and drying. 0.5 g of amino-modified carbon nanotubes, 1.8 g of tetrabutylammonium hydroxide and 50 g of N, N -dimethylformamide, and placed at room temperature for 24 h to allow tetrabutylammonium hydroxide to be fully loaded on the amino-modified carbon nanotubes to obtain surface-modified amino-modified carbon nanotubes.

[0038] 3) Preparation of carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode 0.05 g of surface-modified amino-modified carbon nanotubes, 0.5 g of isopropanol and 3 g of distilled water, 8 g of 2 mol / L hydrochloric acid solution, 0.12 g of aniline and 1 g of 10% ammonium persulfate aqueous solution were placed in a spray bottle to form spray liquid A. 20 mL of 1 mg / mL sulfonated porous foam graphene dispersion was placed in another spray bottle to form spray liquid B.

[0039] Spraying liquid A and spraying liquid B were alternately sprayed on a single side surface of a carbon cloth (size 2 cm×2 cm) to form repeatedly alternately stacked graphene layers and carbon nanotube-grafted polyaniline layers, and spraying one layer of graphene layer and one layer of carbon nanotube-grafted polyaniline layer was counted as one cycle. The cycle was repeated 5 times, and after each cycle, the carbon cloth was frozen with liquid nitrogen, then placed in an ice bath for 3 hours, and then repeatedly washed with deionized water and freeze-dried to obtain a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode.

[0040] The porosity of the composite electrode prepared in Example 3 is 92.90% and the specific surface area is 30.98 m 2 / g, the conductivity is 1.79 S / m. The prepared composite electrode material has a specific capacitance of 178 F / g at a current density of 1 A / g.

[0041] Comparative Example 1 The difference from Example 1 is that the three-dimensional porous foamed graphene obtained in step 1) is not modified with sulfanilic acid, and the three-dimensional porous foamed graphene is directly used in step 3). The porosity of the carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode finally obtained is 93.22%, and the specific surface area is 34.12 m 2 / g, the conductivity is 1.87 S / m. The specific capacitance of the prepared carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode material is 165 F / g at a current density of 1 A / g.

[0042] Comparative Example 2 The difference from Example 1 is that step 2 is omitted and the carbon nanotubes are directly used in step 3), and finally a carbon nanotube / graphene / carbon cloth composite electrode is obtained. The porosity of the composite electrode is 93.91% and the specific surface area is 32.44 m 2 / g, the conductivity is 1.45 S / m. The specific capacitance of the prepared carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode material is 145 F / g at a current density of 1 A / g.

[0043] Comparative Example 3 The difference from Example 1 is that step 1 is omitted) and graphene is directly used in step 3), and finally a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode is obtained. The porosity of the composite electrode is 87.33% and the specific surface area is 26.23 m 2 / g, the conductivity is 1.56 S / m. The specific capacitance of the prepared carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode material is 146 F / g at a current density of 1 A / g.

[0044] The above describes the specific embodiments of the present invention. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art may make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A method for preparing a carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode, characterized in that: The steps include: preparing porous foam graphene; The porous foamed graphene is dispersed in deionized water, sulfanilic acid, sodium nitrite and deionized water are added, and reacted in an ice water bath for 1 to 3 hours, and then concentrated sulfuric acid is added and reacted at 50 to 80° C. to obtain sulfonated porous foamed graphene; Preparation of surface-modified amino-modified carbon nanotubes; The surface-modified amino-modified carbon nanotubes, isopropanol, distilled water, hydrochloric acid, aniline and ammonium persulfate are mixed and reacted to obtain carbon nanotube-grafted polyaniline; The carbon nanotube grafted polyaniline is dispersed in distilled water to obtain a spray liquid A, the sulfonated porous foamed graphene is dispersed in water to obtain a spray liquid B, the spray liquid A and the spray liquid B are alternately sprayed on a single side surface of the carbon cloth to form a graphene layer and a carbon nanotube grafted polyaniline layer that are repeatedly alternately stacked, and the spraying of one graphene layer and one carbon nanotube grafted polyaniline layer is counted as one cycle, and the cycle is repeated multiple times, and after each cycle, the carbon cloth is frozen with liquid nitrogen, and then placed in an ice bath for 2 to 4 hours, and then repeatedly washed with deionized water and freeze-dried at -50°C to obtain a carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode.

2. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 1, characterized in that: The preparation method of the porous foamed graphene is: The pH value of the graphene oxide dispersion is adjusted to 4-5, and a glutaraldehyde aqueous solution is added, mixed and reacted at 50-70° C. to obtain a three-dimensional porous graphene oxide foam; The three-dimensional porous graphene oxide foam is immersed in a hydrazine hydrate aqueous solution, reacted at 80-100° C., and then washed with deionized water until neutral to obtain porous foamed graphene.

3. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 2, characterized in that: The mass concentration of the glutaraldehyde aqueous solution is 20-30%, and the mass ratio of hydrazine hydrate to water in the hydrazine hydrate aqueous solution is 1:(20-25).

4. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 1, characterized in that: The mass ratio of the porous foam graphene to sulfanilic acid is (1-3): (15-20).

5. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 1, characterized in that: The preparation method of the surface-modified amino-modified carbon nanotubes is as follows: The carbon nanotubes are dispersed in concentrated ammonia water and subjected to hydrothermal reaction at 90-100°C to obtain amino-modified carbon nanotubes; The amino-modified carbon nanotubes and tetrabutylammonium hydroxide, N, N -dimethylformamide and mixed evenly, and placed at room temperature for 24 hours to obtain surface-modified amino-modified carbon nanotubes.

6. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 5, characterized in that: The mass ratio of the amino-modified carbon nanotubes to tetrabutylammonium hydroxide is (1-2): (3-6).

7. The method for preparing the carbon nanotube-grafted polyaniline / graphene / carbon cloth composite electrode according to claim 1, characterized in that: In step S3, the mass ratio of carbon nanotubes to aniline is (1-2): (4-7).

8. Use of the carbon nanotube grafted polyaniline / graphene / carbon cloth composite electrode obtained by the preparation method of claim 1 as a flexible electrode material in a supercapacitor.

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