Flexible supercapacitor electrode material and preparation method thereof based on cyclic electrochemical deposition

Abstract

The invention relates to the technical field of electrode materials, in particular to a flexible supercapacitor electrode material and a preparation method thereof based on cyclic electrochemical deposition, and the method comprises the following steps: pretreating flexible carbon cloth to obtain modified carbon cloth; and preparing an aniline electroplating solution and a graphene oxide electroplating solution, and alternately electrodepositing a PANI layer and an rGO layer on the modified carbon cloth to obtain the electrode material with the PANI / rGOR layer. According to the flexible supercapacitor electrode material and the preparation method thereof based on the cyclic electrochemical deposition, the thickness and the proportion of the PANI layer and the rGO layer can be accurately adjusted by controlling the electrodeposition time, the potential and the cycle index, so that the PANI layer and the rGO layer are alternately deposited to form a compact and firmly-combined layered structure, and the flexible supercapacitor electrode material is prepared. And the peeling problem caused by the volume change of the PANI in the charging and discharging process is effectively relieved.

Description

Technical Field

[0001] This invention relates to the field of electrode materials technology, and in particular to a flexible supercapacitor electrode material and its preparation method based on cyclic electrochemical deposition. Background Technology

[0002] With the continuous depletion of fossil fuel reserves and increasing environmental awareness, developing green and efficient energy storage technologies has become an important direction in the energy sector. Supercapacitors, due to their advantages such as high power density, rapid charge and discharge speeds, long cycle life, and environmental friendliness, are considered an important component of next-generation sustainable energy systems. Electrode materials are a key factor determining the performance of supercapacitors; their structural stability and conductivity directly affect the energy density and cycle life of the device. Polyaniline (PANI) is a typical conductive polymer material with high theoretical specific capacitance and good reversible redox properties. However, it is prone to volume expansion and structural pulverization during repeated charge and discharge processes, leading to damage to the conductive network and thus causing a decline in cycle performance. Graphene oxide (GO) and its reduced form (rGO) possess excellent conductivity, large specific surface area, and flexibility, and can be used as carrier materials to improve the conductivity and structural stability of PANI.

[0003] However, traditional PANI / rGO composite electrodes are mostly prepared using chemical oxidative polymerization, resulting in inhomogeneous film structures and poor interfacial adhesion. Furthermore, the complex and costly preparation process of rGO limits its widespread application in flexible energy storage devices. Therefore, how to construct PANI / rGO composite electrodes with high conductivity, excellent adhesion, and long-term cycling stability on flexible carbon cloth substrates has become a pressing technical problem to be solved in the field of flexible supercapacitors. Summary of the Invention

[0004] The purpose of this invention is to provide a flexible supercapacitor electrode material and its preparation method based on cyclic electrochemical deposition. By controlling the electrodeposition time, potential and number of cycles, the thickness and ratio of the PANI layer and the rGO layer can be precisely adjusted, so that the PANI layer and the rGO layer are deposited alternately to form a dense and firmly bonded layered structure, which effectively alleviates the problem of PANI peeling off due to volume changes during charging and discharging, significantly improves the overall performance of the electrode and reduces the preparation cost.

[0005] To achieve the above objectives, this invention provides a method for preparing flexible supercapacitor electrode materials based on cyclic electrochemical deposition, comprising the following steps: S1. Immerse the flexible carbon cloth in the mixed acid solution and let it stand. After taking it out, wash it repeatedly with deionized water until it is neutral. After drying, the modified carbon cloth is obtained. S2. Add aniline to sulfuric acid solution, sonicate to obtain aniline electroplating solution for later use, add graphene oxide to deionized water, sonicate to obtain graphene oxide electroplating solution for later use. S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a counter electrode and a reference electrode, a three-electrode system is assembled. S4. Place the working electrode in the three-electrode system in S3 into the aniline electroplating solution obtained in S2. After electrodeposition and drying, obtain the PANI layer. Then place the working electrode in the graphene oxide electroplating solution obtained in S2. Deposit the rGO layer in situ on the surface of the PANI layer. After drying, obtain the PANI / rGO layer. S5. Repeat step S4 to obtain PANI / rGO. R The electrode material of the layer, R is the number of cycles in step S4.

[0006] Preferably, in S1, the mixed acid solution is concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, the standing temperature is 20-30℃, the standing time is 20-40 min, and the drying temperature is 50-70℃.

[0007] Preferably, in S2, the ultrasonic time is 20-40 min and the ultrasonic temperature is 50-70℃.

[0008] Preferably, in S2, the concentration of the aniline electroplating solution is 0.1-1 mol / L, and the concentration of the graphene oxide electroplating solution is 0.5-2 mg / mL.

[0009] Preferably, in S3, the counter electrode is a platinum wire and the reference electrode is a saturated calomel electrode.

[0010] Preferably, in S4, the electrodeposition time is 10-60 s and the electrodeposition potential is -1.5 V to 1.5 V.

[0011] Preferably, in step S4, the drying temperature is 80-100℃ and the drying time is 2-10 min.

[0012] Preferably, in S4, the electrodeposition time and electrodeposition potential of the PANI layer and the rGO layer are the same.

[0013] Preferably, in S5, R is 5-45.

[0014] The electrode material prepared by the above-mentioned method for preparing flexible supercapacitor electrode materials based on cyclic electrochemical deposition, PANI / rGO R The layers consist of alternating PANI and rGO layers to form a dense and uniform composite conductive structure.

[0015] Therefore, the present invention employs the above-mentioned flexible supercapacitor electrode material and its preparation method based on cyclic electrochemical deposition, and its beneficial effects are as follows: 1. The preparation method provided by the present invention can precisely adjust the thickness and ratio of the PANI layer and the rGO layer by controlling the electrodeposition time, potential and cycle number, so that the PANI layer and the rGO layer are deposited alternately to form a dense and firmly bonded layered structure, which effectively alleviates the peeling problem of PANI caused by volume change during charging and discharging, thereby significantly improving the structural stability and cycle life of the electrode. 2. The electrode material prepared by this invention combines the pseudocapacitive properties of PANI with the high conductivity of rGO, PANI / rGO R The introduction of rGO in the layer creates a highly conductive network, which promotes the rapid transport of electrons. At the same time, the porous nature of the PANI layer is conducive to the diffusion of electrolyte ions, so that the electron and ion transport processes are synergistically optimized. It has both high specific capacitance and excellent rate performance, and exhibits good conductivity and electrochemical stability. 3. The preparation method provided by this invention is completed at room temperature or low temperature, without the need for high-temperature annealing or the use of strong oxidizing or reducing agents, thus avoiding damage to the flexible carbon cloth, ensuring the flexibility and mechanical stability of the electrode material, and the raw materials are readily available and the operation is simple, reducing the preparation cost. 4. The electrode material prepared by this invention uses flexible carbon cloth as a substrate, which can endow the electrode with excellent mechanical flexibility and foldability, meeting the application requirements of flexible energy storage devices.

[0016] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0017] Figure 1 These are combined electrochemical performance diagrams of the electrode materials in Examples 1-4 of this invention, wherein... Figure 1 (a) in the figure is the cyclic voltammetry scan curve of Examples 1-4. Figure 1 (b) in the figure is the constant current charge-discharge curve of Examples 1-4; Figure 2 This is a combined diagram of the electrochemical performance of the electrode materials in Example 3 and Comparative Examples 1-3 of the present invention, wherein... Figure 2 (a) in the figure is the cyclic voltammetry scan curve of Example 3 and Comparative Examples 1-3. Figure 2 (b) in the figure is the constant current charge-discharge curve of Example 3 and Comparative Examples 1-3; Figure 3 PANI / rGO in Example 3 30 SEM images at 1KX; Figure 4 PANI / rGO in Example 3 30 SEM images at 10KX; Figure 5PANI / rGO in Example 3 30 The XPS combination diagram, in which, Figure 5 a) in the diagram is the C1s energy spectrum; Figure 5 b) in the diagram is the N1s energy spectrum. Detailed Implementation

[0018] The present invention will be further described below with reference to the accompanying drawings and embodiments. Unless otherwise defined, the technical or scientific terms used in this invention should be understood in their ordinary sense by those skilled in the art. The features mentioned above or in the specific examples mentioned in this invention can be combined arbitrarily, and these specific embodiments are only used to illustrate the invention and are not intended to limit the scope of the invention.

[0019] This invention provides a method for preparing flexible supercapacitor electrode materials based on cyclic electrochemical deposition, comprising the following steps: S1. Immerse the flexible carbon cloth in the mixed acid solution and let it stand. After taking it out, wash it repeatedly with deionized water until it is neutral. After drying, the modified carbon cloth is obtained. S2. Add aniline to sulfuric acid solution, sonicate to obtain aniline electroplating solution for later use, add graphene oxide to deionized water, sonicate to obtain graphene oxide electroplating solution for later use. S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a counter electrode and a reference electrode, a three-electrode system is assembled. S4. The working electrode in the three-electrode system of S3 is placed in the aniline electroplating solution obtained in S2. After electrodeposition and drying, a PANI layer is obtained. Then, the working electrode is placed in the graphene oxide electroplating solution obtained in S2, and an rGO layer is deposited in situ on the surface of the PANI layer. After drying, a PANI / rGO layer is obtained. The PANI layer and the rGO layer are deposited in situ on the surface of the modified carbon cloth under electrochemical action, forming a tightly bonded composite interface, which effectively avoids the problem of interlayer peeling caused by weak interactions in traditional chemical composites.

[0020] S5. Repeat step S4 to obtain PANI / rGO. R The electrode material of the layer, R is the number of cycles in step S4. Polyaniline (PANI) layers and graphene oxide (GO) layers are alternately deposited on a modified carbon cloth substrate, and the in-situ layer-by-layer construction of PANI / rGO is achieved through electrochemical control. By setting a fixed electrodeposition time and number of cycles R, the thickness and ratio of the PANI and rGO layers can be controlled and adjusted.

[0021] In some embodiments of the present invention, in S1, the mixed acid solution is concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, the standing temperature is 20-30°C, the standing time is 20-40 min, and the drying temperature is 50-70°C.

[0022] In some embodiments of the present invention, in S2, the ultrasonic time is 20-40 min and the ultrasonic temperature is 50-70℃.

[0023] In some embodiments of the present invention, in S2, the concentration of the aniline electroplating solution is 0.1-1 mol / L, and the concentration of the graphene oxide electroplating solution is 0.5-2 mg / mL.

[0024] In some embodiments of the present invention, in S3, the counter electrode is a platinum wire and the reference electrode is a saturated calomel electrode.

[0025] In some embodiments of the present invention, in step S4, the electrodeposition time is 10-60 s and the electrodeposition potential is -1.5 V to 1.5 V. By controlling the electrodeposition time and deposition potential, the thicknesses of the PANI layer and the rGO layer can be precisely adjusted.

[0026] In some embodiments of the present invention, in step S4, the drying temperature is 80-100°C and the drying time is 2-10 minutes. A short drying period is performed after each deposition to ensure tight interlayer bonding and the formation of a stable composite interface structure.

[0027] In some embodiments of the present invention, in S4, the electrodeposition time and electrodeposition potential of the PANI layer and the rGO layer are the same.

[0028] In some embodiments of the present invention, in S5, R is 5-45.

[0029] In some embodiments of the present invention, the electrode material prepared by the above-described method for preparing flexible supercapacitor electrode materials based on cyclic electrochemical deposition, PANI / rGO R The layers consist of alternating PANI and rGO layers to form a dense and uniform composite conductive structure.

[0030] Example 1 S1, with an area of ​​2cm 2 Flexible carbon cloth was immersed in a mixed acid solution at 25°C for 30 minutes. The mixed acid solution consisted of 95% concentrated nitric acid and 98% concentrated sulfuric acid in a 1:1 volume ratio. After removal, it was repeatedly washed with deionized water until neutral, and then dried at 60°C to obtain modified carbon cloth.

[0031] S2. Add 0.456 mL of aniline to 50 mL of 1 M sulfuric acid solution, and sonicate at 65 °C for 30 min to obtain an aniline electroplating solution for later use. Add 50 mg of graphene oxide to 50 mL of deionized water, and sonicate for 30 min to obtain a graphene oxide electroplating solution for later use.

[0032] S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a platinum wire counter electrode and a saturated calomel electrode as the reference electrode, a three-electrode system is assembled.

[0033] S4. Place the working electrode from the three-electrode system in S3 into the aniline electroplating solution obtained in S2. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI layer is obtained. Then, place the working electrode into the graphene oxide electroplating solution obtained in S2 to deposit an rGO layer in situ on the surface of the PANI layer. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI / rGO layer is obtained.

[0034] S5. Repeat step S4 electrodeposition 10 times to obtain PANI / rGO. 10 Electrode material of the layer.

[0035] Example 2 S1, with an area of ​​2cm 2 Flexible carbon cloth was immersed in a mixed acid solution at 25°C for 30 minutes. The mixed acid solution consisted of 95% concentrated nitric acid and 98% concentrated sulfuric acid in a 1:1 volume ratio. After removal, it was repeatedly washed with deionized water until neutral, and then dried at 60°C to obtain modified carbon cloth.

[0036] S2. Add 0.456 mL of aniline to 50 mL of 1 M sulfuric acid solution, and sonicate at 65 °C for 30 min to obtain an aniline electroplating solution for later use. Add 50 mg of graphene oxide to 50 mL of deionized water, and sonicate for 30 min to obtain a graphene oxide electroplating solution for later use.

[0037] S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a platinum wire counter electrode and a saturated calomel electrode as the reference electrode, a three-electrode system is assembled.

[0038] S4. Place the working electrode from the three-electrode system in S3 into the aniline electroplating solution obtained in S2. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI layer is obtained. Then, place the working electrode into the graphene oxide electroplating solution obtained in S2 to deposit an rGO layer in situ on the surface of the PANI layer. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI / rGO layer is obtained.

[0039] S5. Repeat step S4 electrodeposition 20 times to obtain PANI / rGO. 20 Electrode material of the layer.

[0040] Example 3 S1, with an area of ​​2cm 2Flexible carbon cloth was immersed in a mixed acid solution at 25°C for 30 minutes. The mixed acid solution consisted of 95% concentrated nitric acid and 98% concentrated sulfuric acid in a 1:1 volume ratio. After removal, it was repeatedly washed with deionized water until neutral, and then dried at 60°C to obtain modified carbon cloth.

[0041] S2. Add 0.456 mL of aniline to 50 mL of 1 M sulfuric acid solution, and sonicate at 65 °C for 30 min to obtain an aniline electroplating solution for later use. Add 50 mg of graphene oxide to 50 mL of deionized water, and sonicate for 30 min to obtain a graphene oxide electroplating solution for later use.

[0042] S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a platinum wire counter electrode and a saturated calomel electrode as the reference electrode, a three-electrode system is assembled.

[0043] S4. Place the working electrode from the three-electrode system in S3 into the aniline electroplating solution obtained in S2. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI layer is obtained. Then, place the working electrode into the graphene oxide electroplating solution obtained in S2 to deposit an rGO layer in situ on the surface of the PANI layer. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI / rGO layer is obtained.

[0044] S5. Repeat step S4 electrodeposition 30 times to obtain PANI / rGO. 30 Electrode material of the layer.

[0045] Example 4 S1, with an area of ​​2cm 2 Flexible carbon cloth was immersed in a mixed acid solution at 25°C for 30 minutes. The mixed acid solution consisted of 95% concentrated nitric acid and 98% concentrated sulfuric acid in a 1:1 volume ratio. After removal, it was repeatedly washed with deionized water until neutral, and then dried at 60°C to obtain modified carbon cloth.

[0046] S2. Add 0.456 mL of aniline to 50 mL of 1 M sulfuric acid solution, and sonicate at 65 °C for 30 min to obtain an aniline electroplating solution for later use. Add 50 mg of graphene oxide to 50 mL of deionized water, and sonicate for 30 min to obtain a graphene oxide electroplating solution for later use.

[0047] S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a platinum wire counter electrode and a saturated calomel electrode as the reference electrode, a three-electrode system is assembled.

[0048] S4. Place the working electrode from the three-electrode system in S3 into the aniline electroplating solution obtained in S2. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI layer is obtained. Then, place the working electrode into the graphene oxide electroplating solution obtained in S2 to deposit an rGO layer in situ on the surface of the PANI layer. The electrodeposition potential is -1.5V to 1.5V, and the electrodeposition time is 40s. After drying at 90℃ for 5min, a PANI / rGO layer is obtained.

[0049] S5. Repeat step S4 electrodeposition 40 times to obtain PANI / rGO. 40 Electrode material of the layer.

[0050] Comparative Example 1 The difference between this comparative example and Example 3 is that only the aniline electroplating solution is prepared in S2, and in step S4, the working electrode from the three-electrode system in S3 is placed into the aniline electroplating solution obtained in S2, the electrodeposition potential is from -1.5V to 1.5V, the electrodeposition time is 1200s, and the electrodeposition is carried out at 90°C for 5min to obtain the PANI electrode material. Step S5 is omitted, and the rest of the steps are the same as in Example 3.

[0051] Comparative Example 2 The difference between this comparative example and Example 3 is that in step S4, the working electrode in the three-electrode system of S3 is placed in the aniline electroplating solution obtained in S2, with an electrodeposition potential of -1.5V to 1.5V, electrodeposition for 1200s, and drying at 90°C for 5min to obtain the PANI layer. Subsequently, the working electrode is placed in the graphene oxide electroplating solution obtained in S2, and an rGO layer is deposited in situ on the surface of the PANI layer with an electrodeposition potential of -1.5V to 1.5V, electrodeposition for 1200s, and drying at 90°C for 5min to obtain the PANI / rGO electrode material. The rest of the steps are the same as in Example 3.

[0052] Comparative Example 3 The difference between this comparative example and Example 3 is that in step S2, 0.456 mL of aniline and 50 mg of graphene oxide powder are added to 50 mL of 1 M sulfuric acid solution and ultrasonically cleaned for 30 min to ensure uniform mixing, thus obtaining an aniline / GO electroplating solution. In step S4, the working electrode from the three-electrode system in S3 is placed into the aniline / GO electroplating solution obtained in S2, with an electrodeposition potential of -1.5 V to 1.5 V, electrodeposition for 1200 s, and drying at 90 °C for 5 min to obtain a PANI-rGO composite electrode.

[0053] Performance testing a. In a 1M H₂SO₄ electrolyte, a saturated calomel electrode was used as the reference electrode, a platinum wire as the counter electrode, and the electrode materials from Examples 1-4 and Comparative Examples 1-3 were used as the working electrodes. The electrochemical performance was tested using a three-electrode system. The stable operating potential range was -0.2V to 0.8V, and the electrode strength was 5mA / cm². 2 The area specific capacitance obtained at the current density is shown in Table 1.

[0054] Table 1. Area-to-capacitance ratio of electrode materials in Examples 1-4 and Comparative Examples 1-3

[0055] As shown in Table 1, compared with Examples 1, 2, and 4, the areal capacitance of Example 3 reaches 1993.2678 mF / cm². 2 This is the highest value among all embodiments, indicating that the preparation method provided by the present invention can effectively promote the continuity of the conductive network and the full utilization of charge storage active sites. Comparing the performance of Example 3 with Comparative Examples 1-3 reveals that the capacitance performance of Example 3 is significantly higher than that of Comparative Example 3 (1362.6033 mF / cm). 2 The efficiency was increased by approximately 46.28%, demonstrating a significant performance advantage. This proves that the cyclic deposition method proposed in this invention, compared to the electrochemical deposition methods in Comparative Examples 1-3, can significantly improve the electrochemical energy storage performance of flexible electrode materials, exhibiting excellent technical effects and practical application value.

[0056] b. Cyclic scanning of the electrode materials prepared in Examples 1-4 at a scan rate of 100 mV / s in the potential range of -0.2 V to 0.8 V and at 5 mA / cm 2 The results of charge-discharge tests at current densities in the potential range of -0.2V to 0.8V are as follows: Figure 1 As shown. By Figure 1 As can be seen in (a), all four curves have a rectangular shape with superimposed redox peaks, indicating that the electrode materials in Examples 1-4 all have pseudocapacitive characteristics, but PANI / rGO 30 The largest area indicates a larger specific capacitance. (From...) Figure 1 As can be seen in (b), PANI / rGO 30 The longest charge / discharge time visually demonstrates the performance of PANI / rGO. 30 Excellent electrochemical performance.

[0057] PANI / rGO prepared in Example 3 30 The cyclic voltammetric scan curves of the electrodes of Comparative Examples 1-3 at a scan rate of 100 mV / s in the potential range of -0.2 V to 0.8 V and at 5 mA / cm²... 2The constant current charge-discharge curves in the potential range of -0.2V to 0.8V under current density are as follows: Figure 2 As shown. It can be seen that, under the same charge-discharge time conditions as Comparative Examples 1-3, the PANI / rGO in Example 3... 30 The results are significantly superior to the electrodes prepared in Comparative Examples 1-3. It is evident that the composite electrode prepared by the cyclic electrodeposition method provided by this invention combines the pseudocapacitive characteristics of PANI with the high conductivity of rGO, achieving high specific capacitance, good rate performance, and excellent cycling stability.

[0058] c. Regarding PANI / rGO in Example 3 30 SEM testing was performed, and the results were as follows: Figure 3 and Figure 4 As shown. It can be seen that PANI / rGO 30 It exhibits a three-dimensional interconnected porous network structure, which prevents graphene layer aggregation, provides a large specific surface area and relatively low density, and significantly increases the active sites for PANI growth.

[0059] d. Regarding PANI / rGO in Example 3 30 The XPS test was performed, and the results are as follows: Figure 5 As shown. According to Figure 5 As can be seen in a), PANI / rGO 30 The C1s XPS spectrum showed four fitted peaks, which were attributed to C=C bond (284.7 eV), CN bond (285.6 eV), C-OH bond (286 eV) and O=CO bond (288.8 eV), respectively. The presence of CN proved the complexation of PANI and rGO, while the CO peak with lower peak intensity confirmed that GO was reduced to rGO. Figure 5 b) in the text refers to PANI / rGO. 30 The high-resolution N1s spectrum can be divided into three fitted peaks, corresponding to -N = (398.9 eV), -NH- (399.4 eV), and -NH... + - (400.2 eV) indicates that most of the N atoms in PANI exist in the form of phenylpropylamine (-NH-).

[0060] Therefore, the present invention employs the above-mentioned flexible supercapacitor electrode material and its preparation method based on cyclic electrochemical deposition. By controlling the electrodeposition time, potential and number of cycles, the thickness and ratio of the PANI layer and the rGO layer can be precisely adjusted, so that the PANI layer and the rGO layer are deposited alternately to form a dense and firmly bonded layered structure, effectively alleviating the problem of PANI peeling off due to volume changes during charging and discharging.

[0061] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing flexible supercapacitor electrode materials based on cyclic electrochemical deposition, characterized in that: Includes the following steps: S1. Immerse the flexible carbon cloth in the mixed acid solution and let it stand. After taking it out, wash it repeatedly with deionized water until it is neutral. After drying, the modified carbon cloth is obtained. S2. Add aniline to sulfuric acid solution, sonicate to obtain aniline electroplating solution for later use, add graphene oxide to deionized water, sonicate to obtain graphene oxide electroplating solution for later use. S3. Using the modified carbon cloth obtained in S1 as the working electrode, and setting a counter electrode and a reference electrode, a three-electrode system is assembled. S4. Place the working electrode in the three-electrode system in S3 into the aniline electroplating solution obtained in S2. After electrodeposition and drying, obtain the PANI layer. Then place the working electrode in the graphene oxide electroplating solution obtained in S2. Deposit the rGO layer in situ on the surface of the PANI layer. After drying, obtain the PANI / rGO layer. S5. Repeat step S4 to obtain PANI / rGO. R The electrode material of the layer, R is the number of cycles in step S4.

2. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S1, the mixed acid solution is concentrated nitric acid and concentrated sulfuric acid in a volume ratio of 1:1, the standing temperature is 20-30℃, the standing time is 20-40min, and the drying temperature is 50-70℃.

3. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S2, the ultrasonic time is 20-40 minutes and the ultrasonic temperature is 50-70℃.

4. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S2, the concentration of aniline electroplating solution is 0.1-1 mol / L, and the concentration of graphene oxide electroplating solution is 0.5-2 mg / mL.

5. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S3, the counter electrode is a platinum wire, and the reference electrode is a saturated calomel electrode.

6. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S4, the electrodeposition time is 10-60 s and the electrodeposition potential is -1.5 V to 1.5 V.

7. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S4, the drying temperature is 80-100℃ and the drying time is 2-10 minutes.

8. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S4, the electrodeposition time and electrodeposition potential of the PANI layer and the rGO layer are the same.

9. The method for preparing a flexible supercapacitor electrode material based on cyclic electrochemical deposition according to claim 1, characterized in that: In S5, R is 5-45.

10. A flexible supercapacitor electrode material, characterized in that: The flexible supercapacitor electrode material based on cyclic electrochemical deposition, as described in any one of claims 1-9, is prepared using the method for preparing PANI / rGO. R The layers consist of alternating PANI and rGO layers to form a dense and uniform composite conductive structure.

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