CN116230422A - A preparation method of gauze-like graphene/polyaniline supercapacitor electrode material - Google Patents

Abstract

The invention belongs to the technical field of electrode materials of energy storage devices, and discloses a preparation method of a chiffon-shaped graphene/polyaniline (rGO/PANI) super capacitor electrode material. The invention uses KMnO ₄ Redox reaction with C to grow thin layer MnO on rGO sheet ₂ Then MnO is used ₂ As template agent and oxidant, mnO as redox reaction proceeds ₂ At the same time of initiating aniline oxidative polymerization, soluble Mn is generated ²⁺ And is consumed, thereby the PANI replicates MnO ₂ Template morphology, forming thin layer on rGO sheet layer to form thin layerYarn-like rGO/PANI composite. Compared with PANI, the gauze-like rGO/PANI composite electrode material prepared by the invention has excellent multiplying power performance and cycle stability, and can be applied and popularized in the field of super capacitor electrode materials.

Description

A method for preparing a gauze-like graphene/polyaniline supercapacitor electrode material

Technical Field

The present invention belongs to the technical field of electrode materials for energy storage devices, and in particular, relates to a method for preparing a gauze-like graphene/polyaniline (rGO/PANI) supercapacitor electrode material.

Background Art

PANI is a widely studied supercapacitor electrode material with advantages such as high doping ability, good conductivity, high theoretical specific capacity and good environmental stability. However, since PANI is a typical pseudocapacitor electrode material, it stores and releases charges through the redox reaction of the polymer chain. Its capacitance decays rapidly under high current density, and during continuous charge and discharge, the insertion/extraction of ions causes the volume of PANI to change, resulting in the continuous degradation of the PANI capacitance properties. Researchers have adopted many effective measures to improve the capacitance properties of PANI electrode materials, among which the composite of PANI and graphene (rGO) is a very effective method.

At present, most of the rGO/PANI composite materials reported in literature and patents often use (NH ₄ ) ₂ S ₂ O ₈ as an oxidant to oxidize and polymerize aniline. The prepared rGO/PANI composite material has a thicker layer, and PANI grows vertically on the rGO matrix in a burr-like morphology or forms a composite material with rGO in a fiber-like morphology. (ACS Nano, 2012, 6, 1715–1723. Journal of Physical Chemistry C, 2012, 116, 5420-5426. Electrochimica Acta, 2017, 228, 290–298. Journal of Physics and Chemistry of Solids, 2022, 165, 110673–10689. Patent CN 105694031 A). Although the capacitance properties of these composite materials have been improved, there is still a certain gap from practical application.

In fact, the capacitive properties of electrode materials are closely related to their nanostructures. Therefore, it is very meaningful to design and prepare rGO/PANI composite electrode materials with reasonable nanostructures to improve their capacitive properties.

Summary of the invention

In view of the shortcomings of the prior art, the object of the present invention is to provide a method for preparing a gauze-like graphene/polyaniline (rGO/PANI) supercapacitor electrode material with excellent rate performance and cycle stability.

In order to achieve the above technical purpose, the inventors selected the template agent _MnO2 to oxidize the aniline monomer. _MnO2 is environmentally friendly, the raw materials are easily available, and it is a strong oxidant under acidic conditions. Its reduction potential (1.23V vs. NHE) is higher than the oxidative polymerization potential of the aniline monomer (0.55 V vs. NHE), and it can be used as a solid oxidant for oxidizing the aniline monomer. The overall concept of the present invention is: a thin layer of _MnO2 is grown on the rGO sheet through the redox reaction of _KMnO4 and C, and then _MnO2 is used as a template agent and oxidant. As the redox reaction proceeds, _MnO2 generates soluble Mn2 ⁺ and is consumed while initiating the oxidative polymerization of aniline, so that PANI replicates the _MnO2 template morphology, and a thin layer is generated on the rGO sheet to form a gauze-like rGO/PANI composite material.

Specifically, the purpose of the present invention is achieved according to the following technical solutions:

A method for preparing a gauze-like rGO/PANI supercapacitor electrode material, the method comprising the following steps:

(1) Preparation of gauze-like rGO/MnO ₂ : Add KMnO ₄ to the rGO nanolayer dispersion, stir to dissolve KMnO ₄ , heat under reflux at 70-80°C for 2-3h, wash with water and filter to obtain a gauze-like solid intermediate product rGO/MnO ₂ ;

(2) Preparation of gauze-like rGO/PANI: The gauze-like solid intermediate product rGO/ _MnO2 was added to ultrapure water and ultrasonically dispersed to form a uniform dispersion. After adding aniline monomer, the mixture was stirred for 25 to 40 minutes to allow aniline monomer to reach saturated adsorption on the rGO/ _MnO2 sheet. After precooling in an ice bath, precooled 0.2 to 0.5 mol/L _{H2SO4 solution} was added to adjust the pH of the system to 0.4 to 0.8. The mixture was stirred in an ice bath for 6 to 12 hours. The gauze-like rGO/PANI was obtained after washing with water, washing with alcohol, filtering and freeze-drying.

Further preferably, in the method for preparing the gauze-like rGO/PANI supercapacitor electrode material as described above, the mass ratio of rGO to KMnO ₄ in step (1) is 1:(1.17-2.34).

Further preferably, in the method for preparing the gauze-like rGO/PANI supercapacitor electrode material as described above, the heating reflux temperature in step (1) is 70° C. and the reaction time is 2 h.

Further preferably, the method for preparing the gauze-like rGO/PANI supercapacitor electrode material as described above is characterized in that the temperature of the ice bath in step (2) is 0-5° C. and the reaction time is 6 h.

Further preferably, in the method for preparing the gauze-like rGO/PANI supercapacitor electrode material as described above, in step (2), the pH of the system is adjusted to 0.4 by adding pre-cooled H ₂ SO ₄ solution.

Further preferably, in the method for preparing the gauze-like rGO/PANI supercapacitor electrode material as described above, the preparation method of the rGO nanolayer dispersion described in step (1) is: adding hydrazine hydrate and ammonia water to the graphite oxide nanolayer dispersion system, stirring at room temperature for 20 to 40 minutes, and then continuously stirring for 0.8 to 1.2 hours under oil bath conditions of 94 to 96°C, cooling to room temperature, centrifuging, removing the rGO nanolayer that has not been completely peeled off, and obtaining a stable and uniformly dispersed rGO nanolayer dispersion.

Compared with the prior art, the present invention has the following advantages and significant improvements:

(1) The preparation conditions of this method are mild and the process is controllable. No additional oxidant is required. The aniline monomer grows two-dimensionally along the interface of the _MnO2 nanolayer. The _MnO2 template and the aniline monomer pre-adsorbed and saturated on it react rapidly to form a large number of polymerization centers, causing a large amount of _MnO2 to be consumed in a short period of time, effectively inhibiting the secondary growth process of PANI. PANI successfully replicates the morphology of the template, and the prepared gauze-like rGO/PANI has excellent capacitive properties.

(2) The gauze-like rGO/PANI composite material prepared by this method has the following advantages: the base material rGO has a large specific surface area, and the gauze-like rGO/PANI composite material formed after the growth of the PANI thin layer has abundant electrochemical reaction active sites, which is conducive to the full play of pseudocapacitance; the excellent conductivity of rGO ensures that the composite material has good conductivity when PANI is in an insulating state, which is conducive to the rapid transmission of electrons; the unique structural flexibility of rGO plays an effective buffering role in the volume change of PANI in the electrochemical reaction. Therefore, compared with PANI, the gauze-like rGO/PANI composite electrode material has excellent rate performance and cycle stability, and can be applied and promoted in the field of supercapacitor electrode materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an XRD spectrum of rGO (a) prepared in Comparative Example 1 of the present invention, rGO/MnO ₂ -1 (b) and rGO/PANI-1 (c) prepared in Example 1;

Figure 2 is TEM photos of rGO prepared in Comparative Example 1 of the present invention (a), rGO/MnO ₂ -1 prepared in Example 1 (b), rGO/MnO ₂ -2 prepared in Example 2 (c), and rGO/MnO ₂ -C1 prepared in Comparative Example 2 (d);

FIG3 is a TEM photograph of rGO/PANI-1 (a) prepared in Example 1 of the present invention, rGO/PANI-2 (b) prepared in Example 2, and rGO/PANI-C1 (c) prepared in Comparative Example 2;

FIG4 is a FESEM photograph of rGO/PANI-1 (a) prepared in Example 1 of the present invention, rGO/PANI-2 (b) prepared in Example 2, and rGO/PANI-C1 (c) prepared in Comparative Example 2;

FIG5 is a surface scan photograph of C, O, and N elements of rGO/PANI-1 prepared in Example 1 of the present invention;

FIG6 is a FESEM image of rGO/PANI-3 prepared in Example 3 of the present invention;

FIG7 is a FESEM photograph of rGO/PANI-4 prepared in Example 4 of the present invention;

FIG8 is a FESEM image of rGO/PANI-5 prepared in Example 5 of the present invention;

FIG9 is a FESEM image of rGO/PANI-6 prepared in Example 6 of the present invention;

Figure 10 is a constant current charge-discharge curve of rGO/PANI-1, rGO/PANI-2 and rGO/PANI-C1 prepared in Example 1, Example 2 and Comparative Example 2 of the present invention at current densities of 0.25 A/g (a) and 10 A/g (b), and a capacitance retention rate diagram in the current density range of 0.25 to 10 A/g (c);

FIG11 is a constant current charge-discharge curve of rGO prepared in Comparative Example 1 at a current density of 0.25 A/g;

Figure 12 is a FESEM photo of rGO/PANI-C2 prepared in Comparative Example 3 (a) and constant current charge and discharge curves at current densities of 0.25 A/g (b) and 10 A/g (c);

Figure 13 is a FESEM photo of rGO/PANI-C3 prepared in Comparative Example 4 (a) and constant current charge and discharge curves at current densities of 0.25 A/g (b) and 10 A/g (c);

Figure 14 is a FESEM photo of PANI prepared in Comparative Example 5 (a) and constant current charge and discharge curves at current densities of 0.25 A/g (b) and 10 A/g (c);

DETAILED DESCRIPTION

Below in conjunction with accompanying drawings and attached table and embodiment, technical scheme of the present invention is clearly and completely described, the following examples are only used to illustrate the present invention, and should not be regarded as limiting the scope of protection of the present invention. In addition, those who do not indicate specific technical operation steps or conditions in the embodiment are all carried out according to the technology or conditions described in the document in this area or according to the product specification. Those who do not indicate the manufacturer of reagents used or instruments are all conventional products that can be obtained by commercial purchase.

It should be noted that the preparation of the working electrode and the electrochemical test method are as follows:

A working electrode was prepared using the sample obtained in the example of the present invention: 3 mg of active material was weighed and added to an agate mortar in a mass ratio of 90%:5%:5% of active material: acetylene black: polytetrafluoroethylene binder. An appropriate amount of ethanol was added and ground into a paste. The paste was evenly spread on a 1 cm×1 cm stainless steel mesh to form a sandwich structure. The paste was baked in an oven at 60°C for 10 h and then pressed into a tablet (pressure of 5 MPa).

The electrochemical test adopts a three-electrode system, with the electrode prepared by the above method as the working electrode, the platinum sheet as the counter electrode, and the Ag/AgCl electrode as the reference electrode. In a 1 mol/L _{H2SO4 electrolyte} , the mass specific capacitance of the electrode material is calculated by testing the constant current charge and discharge curve, and the capacitance retention and cycle stability of the electrode material are calculated based on this.

Example 1: Preparation of gauze-like rGO/PANI-1

(1) To 100 mL of 0.25 mg/mL GO nanolayer dispersion system, 34 μL (50%) hydrazine hydrate and 200 μL (25%) ammonia water were added, and the mixture was stirred at room temperature for 30 min. The oil bath temperature was raised to 95 °C and stirred for 1 h. The mixture was then cooled to room temperature and centrifuged at 3000 rpm for 30 min to remove the rGO nanolayer that was not completely peeled off, thereby obtaining a stable and uniformly dispersed rGO nanolayer dispersion.

(2) Add 20 mg KMnO ₄ to 95 mL of the rGO nanolayer dispersion obtained in step (1) and stir to dissolve, then heat under reflux at 70° C. and stir to react for 2 h, wash with water and filter to obtain solid rGO/MnO ₂ -1.

(3) Add 30 mL of ultrapure water to the rGO/ _MnO2-1 obtained in step (2), and disperse by ultrasonication for 30 min to form a uniform dispersion. Add 110 μL of aniline and stir for 30 min. After precooling in an ice bath, add ₂₀ mL of precooled _H2SO4 solution with a concentration of 0.2 mol/L, and stir in an ice bath for 6 h. Wash with water, wash with alcohol, filter, and freeze-dry to obtain rGO/PANI-1.

The solid products obtained in steps (2) and (3) were analyzed by XRD patterns. The results are shown in Figures 1(b) and (c). From the attribution of the crystal planes to which the diffraction peaks belong, it can be explained that the intermediate product obtained in step (2) is a composite of rGO and layered MnO ₂ , and the final product obtained in step (3) is a composite of rGO and PANI, which further indicates that MnO ₂ successfully oxidizes polymerized aniline as a self-sacrificial template oxidant. In addition, by performing TEM scanning, the TEM photo of rGO/MnO ₂ -1 is shown in Figure 2(b). It can be seen that the surface of the prepared gauze-like rGO/MnO ₂ -1 is uniform, indicating that the MnO ₂ layer grows uniformly on the rGO sheet, and the layer thickness increases compared with rGO. The TEM and FESEM photo features of rGO/PANI-1 in Figures 3(a) and 4(a) are consistent, indicating that PANI successfully replicates the morphology of the oxidant and finally generates a gauze-like product rGO/PANI. In addition, the elemental surface scanning results further indicate that the PANI thin layer grows uniformly on the rGO sheet. The mass specific capacitance of the rGO/PANI-1 electrode material at 0.25A/g is 435F/g, and the mass specific capacitance at 10A/g is 364F/g, calculated from the constant current charge and discharge curves of Figure 10 (a) and (b). When the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 84%. After 1000 consecutive charge and discharge cycles at 10A/g, the mass specific capacitance is 80% of the initial value.

Example 2: Preparation of gauze-like rGO/PANI-2

(1) To 100 mL of 0.25 mg/mL GO nanolayer dispersion system, 34 μL (50%) hydrazine hydrate and 200 μL (25%) ammonia water were added, and the mixture was stirred at room temperature for 30 min. The oil bath temperature was raised to 95 °C and stirred for 1 h. The mixture was then cooled to room temperature and centrifuged at 3000 rpm for 30 min to remove the rGO nanolayer that was not completely peeled off, thereby obtaining a stable and uniformly dispersed rGO nanolayer dispersion.

(2) Add 40 mg KMnO ₄ to 95 mL of the rGO nanolayer dispersion obtained in step (1) and stir to dissolve, then heat under reflux at 70° C. and stir to react for 2 h, wash with water and filter to obtain solid rGO/MnO ₂ -2.

(3) The rGO/ _MnO2-2 obtained in step (2) was added with 30 mL of ultrapure water and ultrasonically dispersed for 30 min to form a uniform dispersion, 110 μL of aniline was added and stirred for 30 min, and after precooling in an ice bath, 20 _mL of precooled _H2SO4 solution with a concentration of 0.2 mol/L was added, and the mixture was stirred in an ice bath for 6 h. After washing with water, washing with alcohol, filtering and freeze-drying, rGO/PANI-2 was obtained.

The solid product obtained in step (2) was scanned by TEM. The TEM photo of rGO/MnO ₂ -2 is shown in Figure 2(c). The MnO ₂ layer grows uniformly on the rGO sheet, and the thickness is increased compared with rGO/MnO ₂ -1. The TEM and FESEM photo features of rGO/PANI-2 in Figures 3(b) and 4(b) are consistent, indicating that PANI successfully replicates the morphology of the oxidant to eventually generate a gauze-like product rGO/PANI. Compared with rGO/PANI-1, the thickness of rGO/PANI-2 is increased. The mass specific capacitance of the rGO/PANI-2 electrode material at 0.25A/g is calculated to be 486F/g, and the mass specific capacitance at 10A/g is 370F/g, and when the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 76%. After 1000 cycles of continuous charge and discharge at 10 A/g, the mass specific capacitance was 74% of the initial value. Although the initial capacitance value at low current density increased due to the increase in the PANI layer thickness of the gauze-like rGO/PANI-2, the rate performance and cycle stability decreased slightly.

Example 3: Preparation of gauze-like rGO/PANI-3

In this example, the sample was heated under reflux at 80° C. for 2 h, and other experimental conditions and operation steps were the same as those in Example 2. The FESEM image of the prepared sample rGO/PANI-3 is shown in FIG6 , indicating that gauze-like rGO/PANI can be successfully prepared under this experimental condition.

Example 4: Preparation of gauze-like rGO/PANI-4

In this example, the sample was heated under reflux at 70° C. for 3 h, and the other experimental conditions and operation steps were the same as those in Example 2. The FESEM image of the prepared sample rGO/PANI-4 is shown in FIG7 , indicating that gauze-like rGO/PANI can be successfully prepared under this experimental condition.

Example 5: Preparation of gauze-like rGO/PANI-5

In this example, the ice bath stirring reaction time was changed to 12 h in step (3), and the other experimental conditions and operation steps were the same as those in Example 2. The FESEM image of the prepared sample rGO/PANI-5 is shown in Figure 8, indicating that gauze-like rGO/PANI can be successfully prepared under this experimental condition.

Example 6: Preparation of gauze-like rGO/PANI-6

In this example, the concentration of the pre-cooled 20 mL H ₂ SO ₄ solution was changed to 0.5 mol L ^-1 in step (3), and the other experimental conditions and operation steps were the same as those in Example 2. The FESEM image of the prepared sample rGO/PANI-6 is shown in FIG9 , indicating that gauze-like rGO/PANI can be successfully prepared under this experimental condition.

Comparative Example 1: Preparation of rGO

In this comparative example, the method in step (1) of Example 1 was used to prepare a graphene nanolayer dispersion, which was filtered, washed with water, washed with alcohol, filtered, and freeze-dried to obtain rGO.

The XRD spectrum and TEM photo of the prepared product rGO are shown in Figure 1(a) and Figure 2(a). The diffraction peak in Figure 1(a) is attributed to the characteristic diffraction peak of rGO, and Figure 2(a) clearly shows the wrinkled gauze-like morphology of rGO. The constant current charge and discharge curve of the rGO electrode material at a current density of 0.25A/g is shown in Figure 11. The calculated mass specific capacitance of the rGO electrode material at a current density of 0.25A/g is only 118F/g.

Comparative Example 2: Preparation of rGO/PANI-C1

In this comparative example, the mass of KMnO ₄ added in step (2) was changed to 70 mg, and the experimental conditions and operating steps were the same as those in Example 2.

The FESEM photo of the intermediate product rGO/MnO ₂ -C1 prepared is shown in Figure 2(d), and the TEM and FESEM photos of the final product rGO/PANI-C1 are shown in Figure 3(c) and Figure 4(c). When the amount of KMnO ₄ increases to 70 mg, erected scale-like MnO ₂ nanosheets are generated on the surface of the rGO sheet. The gauze-like morphology of the final product rGO/PANI-C1 disappears, and concave-convex PANI is generated on the surface of rGO, and the layer thickness increases significantly. The mass specific capacitance of the rGO/PANI-C1 electrode material at 0.25A/g is calculated to be 530F/g, and the mass specific capacitance at 10A/g is 298F/g, and when the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 56%. After 1000 consecutive charge and discharge cycles at 10 A/g, the mass specific capacitance was 62% of the initial value. Compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the rate performance and cycle stability of rGO/MnO ₂ -C1 were significantly reduced.

Comparative Example 3: Preparation of rGO/PANI-C2

In this comparative example, the concentration of the pre-cooled 20 mL H ₂ SO ₄ solution was changed to 1 mol/L in step (3), and the experimental conditions and operation steps were the same as those in Example 2.

The FESEM photo and constant current charge-discharge curve of the prepared sample rGO/PANI-C2 are shown in Figure 12. The gauze-like morphology disappears, indicating that the appropriate H ₂ SO ₄ solution concentration in the system plays an important role in the replication of the oxidant morphology of PANI. The mass specific capacitance of the rGO/PANI-C2 electrode material at 0.25A/g is 452F/g, and the mass specific capacitance at 10A/g is 306F/g. When the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 68%. After 1000 consecutive charge and discharge cycles at 10A/g, the mass specific capacitance is 63% of the initial value. Compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the rate performance and cycle stability of rGO/PANI-C2 are significantly reduced.

Comparative Example 4: Preparation of rGO/PANI-C3

(1) The graphene nanolayer dispersion prepared by the method in step (1) of Example 1 was filtered, 30 mL of ultrapure water was added and ultrasonically dispersed for 30 min to form a uniform dispersion, 110 μL of aniline was added and stirred for 30 min, and precooled in an ice bath;

(2) Add 180 mg (NH ₄ ) ₂ S ₂ O ₈ to 20 mL of 0.2 mol/L H ₂ SO ₄ solution, stir to dissolve, and precool in an ice bath;

(3) The solution obtained in step (2) was quickly added to the system of step (1), and the mixture was stirred in an ice bath for 6 h. After washing with water, washing with alcohol, and filtering and drying, rGO/PANI-C3 was obtained.

The solid product was characterized by morphology. The FESEM photo and constant current charge-discharge curve are shown in Figure 13. Brush-like PANI grew on the surface of the rGO sheet, which shows that the _MnO2 template oxidant plays a key role in the formation of gauze-like rGO/PANI composite materials. The mass specific capacitance of the rGO/PANI-C3 electrode material at 0.25A/g is 391F/g, and the mass specific capacitance at 10A/g is 272F/g. When the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 70%. After 1000 times of charge and discharge at 10A/g, the mass specific capacitance is 72% of the initial value. Compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the mass specific capacitance, rate performance and cycle stability of rGO/PANI-C3 are all reduced.

Comparative Example 5: Preparation of PANI

(1) Add 110 μL of aniline to 30 mL of ultrapure water and stir for 30 min. Precool in an ice bath.

(2) Add 180 mg (NH ₄ ) ₂ S ₂ O ₈ to 20 mL of 0.2 mol/L H ₂ SO ₄ solution, stir to dissolve, and precool in an ice bath;

(3) The solution obtained in step (2) is quickly added to the system of step (1), and the mixture is stirred in an ice bath for 6 h. The mixture is washed with water, washed with alcohol, filtered and dried to obtain PANI.

The morphology of the obtained solid product was characterized, and the FESEM photos and constant current charge and discharge curves are shown in Figure 14. PANI is a curved short nanofiber. The mass specific capacitance of the PANI electrode material at 0.25A/g is 532F/g, and the mass specific capacitance at 10A/g is 293F/g. When the current density increases from 0.25A/g to 10A/g, the capacitance retention rate is 55%. After 1000 continuous charge and discharge cycles at 10A/g, the mass specific capacitance is 60% of the initial value. Compared with the gauze-like rGO/PANI-1 and rGO/PANI-2 electrode materials, the rate performance and cycle stability of PANI are significantly reduced.

Table 1 shows the mass specific capacitance, capacitance retention and cycle stability of rGO/PANI-1, rGO/PANI-2, rGO/PANI-C1, rGO/PANI-C2, rGO/PANI-C3 and PANI prepared in Example 1, Example 2, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5 of the present invention.

Table 1

Claims (6)

1. The preparation method of the chiffon rGO/PANI supercapacitor electrode material comprises the following steps:

(1) Gauze-like rGO/MnO ₂ Is prepared from the following steps: adding KMnO into rGO nano-layer dispersion liquid ₄ Stirring to make KMnO ₄ After dissolution, heating, refluxing and stirring for reaction for 2-3 hours at 70-80 ℃, washing and suction filtering to obtain a chiffon-shaped solid intermediate product rGO/MnO ₂ ；

(2) Preparation of chiffon-like rGO/PANI: combining the gauze-like solid intermediate product rGO/MnO ₂ Adding into ultrapure water, performing ultrasonic dispersion to form uniform dispersion, adding aniline monomer, and stirring for 25-40 min to ensure that the aniline monomer is in rGO/MnO ₂ Saturated adsorption is achieved on the sheet layer, and then precooled in an ice bath, and precooled H of 0.2-0.5 mol/L is added ₂ SO ₄ And (3) regulating the pH value of the system to be 0.4-0.8, stirring and reacting for 6-12 h under the ice bath condition, and washing with water, washing with alcohol, filtering, and freeze-drying to obtain the gauze-like rGO/PANI.

2. The method for preparing an electrode material of a Bao Shazhuang rGO/PANI supercapacitor according to claim 1, wherein in the step (1), rGO and KMnO are prepared by ₄ The mass ratio of (2) is 1: (1.17-2.34).

3. The method for preparing the Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein the heating reflux temperature in the step (1) is 70 ℃ and the reaction time is 2 hours.

4. The method for preparing the Bao Shazhuang rGO/PANI supercapacitor electrode material according to claim 1, wherein the temperature of the ice bath in the step (2) is 0-5 ℃ and the reaction time is 6 hours.

5. The method for preparing Bao Shazhuang rGO/PANI super capacitor electrode material as claimed in claim 1, wherein in step (2), pre-cooled H is added ₂ SO ₄ Solution adjustment system ph=0.4.

6. The method for preparing the Bao Shazhuang rGO/PANI super capacitor electrode material according to claim 1, wherein the method for preparing the rGO nano-layer dispersion liquid in the step (1) comprises the following steps: adding hydrazine hydrate and ammonia water into the graphite oxide nano layer dispersion liquid system, stirring for 20-40 min at room temperature, continuously stirring for 0.8-1.2 h under the oil bath condition of 94-96 ℃, cooling to room temperature, centrifuging, and removing the rGO nano layer which is not completely stripped to obtain stable and uniformly dispersed rGO nano layer dispersion liquid.

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