Flexible composite capacitor electrode material and preparation method thereof

Abstract

The invention discloses a flexible composite capacitor electrode material and a preparation method thereof, and relates to the technical field of flexible electronic materials. When the flexible composite capacitor electrode material is prepared, graphene oxide is subjected to a bromination reaction to prepare a graphene oxide initiator, the graphene oxide initiator reacts with sodium p-styrenesulfonate and (4-vinyl phenyl) methylamine hydrochloride to prepare GO-copolymerized PSS, rGO-copolymerized PSS is obtained after reduction, and then the rGO-copolymerized PSS and 3, 4-ethylenedioxythiophene are polymerized to prepare a PEDOT: rGO-copolymerized PSS coating solution; the preparation method comprises the following steps: treating aluminum foil with hydrogen peroxide and ammonium hydroxide to obtain hydroxylated aluminum foil, modifying with silane to obtain modified aluminum foil, spin-coating a coating solution, and carrying out heat treatment to form aerogel coating aluminum foil; and finally, growing a zirconium-based metal organic framework on the aerogel coating aluminum foil and complexing manganese ions to prepare the flexible composite capacitor electrode material. The flexible composite capacitor electrode material prepared by the invention has excellent flexibility, high specific capacitance and cycling stability.

Description

Technical Field

[0001] This invention relates to the field of flexible electronic materials technology, specifically to a flexible composite capacitor electrode material and its preparation method. Background Technology

[0002] Flexible composite capacitor electrode materials are one of the core components of flexible electronic devices, and their performance directly determines the energy density, power density, mechanical flexibility, and cycle stability of the capacitor. An ideal flexible electrode needs to possess high conductivity, abundant active sites, and the ability to maintain stable performance under significant bending or stretching. Currently, such electrodes are often fabricated by combining carbon-based materials, conductive polymers, or metal oxides with flexible substrates. However, a single material often cannot simultaneously meet multiple requirements. Furthermore, ensuring a strong, low-contact-resistance bond between the active material and the flexible substrate, and constructing an efficient ion-electron co-transport network, remains a technological challenge.

[0003] In recent years, with the rapid development of the Internet of Things, artificial intelligence, and wearable health monitoring technologies, the market has placed unprecedented demands on thin, flexible, efficient, and durable energy storage devices. This has driven the development of flexible capacitors towards higher overall performance, requiring not only higher specific capacitance and rate performance of the electrodes, but also stable operation under complex mechanical deformation. Therefore, developing a fabrication method that can effectively integrate a highly conductive framework, a highly pseudocapacitive active material, and a porous conductive framework, and integrate them onto a flexible metal foil through robust interface engineering, has become key to overcoming the current performance bottlenecks of flexible electrodes. This design aims to synergistically improve the material's charge storage capacity, mechanical integrity, and interface stability, which is of great significance for promoting the development of next-generation high-performance flexible electronic devices. Summary of the Invention

[0004] The purpose of this invention is to provide a flexible composite capacitor electrode material and its preparation method to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A flexible composite capacitor electrode material, comprising a modified aluminum foil having a PEDOT:rGO-copolymer PSS composite aerogel coating and a zirconium-based metal-organic framework with manganese ion active sites sequentially coated and grown on its surface.

[0006] As an optimization, the PEDOT:rGO-copolymer PSS composite aerogel coating is prepared by brominating graphene oxide to obtain graphene oxide initiator, reacting it with sodium p-styrene sulfonate and (4-vinylphenyl)methylamine hydrochloride and reducing it to obtain rGO-copolymer PSS, and then polymerizing it with 3,4-ethylenedioxythiophene.

[0007] As an optimization, the zirconium-based metal-organic framework with manganese ion active sites is prepared by growing the zirconium-based metal-organic framework in the aerogel pores and complexing manganese ions.

[0008] As an optimization, the modified aluminum foil is prepared by treating aluminum foil with hydrogen peroxide and ammonium hydroxide and then modifying it with silane.

[0009] A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed at a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105), stirred at 25~30℃ and 300~500r / min for 40~50h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator and sodium p-styrene sulfonate were mixed. (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine, and an ethanol / water mixture (V / V=1:1) were mixed in a mass ratio of 1:(2.2~2.6):(0.5~0.7):(0.06~0.07):(195~205). Copper bromide (0.04~0.05 by mass of graphene oxide initiator) was added, and the mixture was stirred at 40~50℃ and 500~700 r / min for 10~14 h. After dialyzing with deionized water for 3~4 days, the mixture was freeze-dried to obtain GO-copolymer PS. S; reduce GO-copolymer PSS to obtain rGO-copolymer PSS; weigh rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate and ferrous sulfate heptahydrate at a mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005), add rGO-copolymer PSS to deionized water at 0.2wt%~0.3wt%, and sonicate for 20~40 min to obtain rGO-copolymer PSS dispersion; under a nitrogen atmosphere, add rGO... - The copolymer PSS dispersion was sequentially added with 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate, and stirred at 25-30℃ and 500-700 r / min for 20-28 h. After dialyzing with deionized water for 3-4 days, the mixture was freeze-dried to obtain PEDOT:rGO-copolymer PSS. The PEDOT:rGO-copolymer PSS was added at 1.4wt%-1.8wt% to deionized water and stirred at 25-35℃ and 500-700 r / min for 20-40 min to obtain the coating solution. (2) Hydrogen peroxide and ammonium hydroxide are mixed evenly at a volume ratio of 1:(2.8~3.2), diluted with deionized water to 20 vol%, and stirred at 25~30℃ and 300~500 r / min for 10~14 h to obtain a mixed treatment solution; aluminum foil is immersed in the mixed treatment solution and stirred at 25~30℃ and 300~500 r / min for 50~70 min, then removed, washed with ethanol and deionized water, and dried to obtain hydroxylated aluminum foil; γ- A 0.04-0.05M silane modification solution was prepared by dissolving aminoethylaminopropyltrimethoxysilane in dichloromethane; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 25-30℃ and 300-500 r / min for 70-75 h, washed with deionized water, and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, and treated at 175-185℃ for 1.5-2.5 h in a nitrogen atmosphere, followed by freeze-drying to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:(95~100):(50~60), stir at 125~135℃ and 300~500r / min for 1.5~2.5h, cool, add 1~1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain MOF / aerogel-coated aluminum foil; dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 0.7wt%~1wt%, add MOF / aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0010] As an optimization, the graphene oxide in step (1) has a thickness of ≤5nm and a sheet diameter of 10μm, and was purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.

[0011] As an optimization, the specific method for reducing GO-copolymer PSS to obtain rGO-copolymer PSS in step (1) is as follows: Under nitrogen protection, GO-copolymer PSS is uniformly dispersed in deionized water at a concentration of 0.5~1.0 mg / mL, ultrasonically treated for 30 min, ascorbic acid with a mass of 7~9 times that of GO-copolymer PSS is added, and the mixture is stirred at 70~80℃ and 300~500 r / min for 4~6 h, washed with deionized water, and dried to obtain rGO-copolymer PSS.

[0012] As an optimization, the PEDOT:rGO-copolymer PSS reaction process in step (1) is as follows: .

[0013] As an optimization, the aluminum foil in step (2) is a commercial aluminum foil with a thickness of 0.03 mm.

[0014] As an optimization, the spin coating method in step (2) is as follows: the coating solution is dripped onto the modified aluminum foil with a syringe to form a film with an initial thickness of about 0.3 mm, and then rotated at 800~900 r / min for 15 s.

[0015] As an optimization, the zirconium propoxide solution in step (3) has a mass percentage of 70 wt%.

[0016] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing flexible composite capacitor electrode materials, this invention involves brominating graphene oxide to obtain a graphene oxide initiator, reacting it with sodium p-styrene sulfonate and (4-vinylphenyl)methylamine hydrochloride to obtain GO-copolymer PSS, reducing it to obtain rGO-copolymer PSS, and then polymerizing it with 3,4-ethylenedioxythiophene to obtain a PEDOT:rGO-copolymer PSS coating solution. Aluminum foil is treated with hydrogen peroxide and ammonium hydroxide to obtain hydroxylated aluminum foil, which is then modified with silane to obtain modified aluminum foil. The coating solution is spin-coated and heat-treated to form an aerogel-coated aluminum foil. Finally, a zirconium-based metal-organic framework is grown on the aerogel-coated aluminum foil and manganese ions are complexed to obtain the flexible composite capacitor electrode material.

[0017] First, this method achieves a multi-level composite structure that combines the excellent conductivity of aluminum, the high specific surface area and flexibility of carbon materials, the high pseudocapacitive properties of conductive polymers, and the structural designability and high activity of MOFs. Surface-modified aluminum foil serves as a flexible current collector, ensuring mechanical support and rapid electron transport at the bottom layer. A PEDOT:rGO-copolymer PSS conductive aerogel coating constructed on its surface forms a three-dimensional interconnected network possessing high conductivity, flexibility, and abundant pseudocapacitive activity. Furthermore, the in-situ growth and introduction of manganese ions into a zirconium-based MOF significantly enhances the overall specific capacity and redox activity of the material. This gradient composite structure allows for the spatially optimized configuration and synergistic enhancement of electron and ion transport and charge storage functions.

[0018] Secondly, by constructing a dual stabilization network combining covalent and ionic crosslinking, a dual improvement in electrode structural integrity and interfacial stability was achieved. On one hand, the covalent grafting between graphene oxide and PSS chains constitutes a robust covalent crosslinking framework, providing fundamental mechanical support for the entire active coating. On the other hand, in the final manganese ion treatment step, manganese ions not only act as active sites embedded in the MOF framework but also coordinate with sulfonate groups on the PSS chains and PEDOT, forming a broad ionic crosslinking network between PSS and PEDOT, and between the PEDOT:rGO-copolymer PSS composite coating and the amino-containing aluminum foil substrate. This not only significantly enhances the electrode's mechanical flexibility and cycling stability but also simultaneously constructs and optimizes continuous electron transport paths and rapid ion transport paths throughout the electrode, thereby ensuring high-rate performance and long-life cycling under high loads. Detailed Implementation

[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail.

[0021] Example 1: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed in a mass ratio of 1:0.02:8.5:17:95, stirred at 25°C and 300 r / min for 40 h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator, sodium p-styrenesulfonate, (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine and ethanol / water mixed solvent (V / V=1:1) were mixed in a mass ratio of 1:2.2:0.5:0.06:195, and 0.04% copper bromide of graphene oxide initiator were added, stirred at 40°C and 500 r / min for 10 h, dialyzed with deionized water for 3 days, and freeze-dried to obtain GO-copolymer PSS; GO- rGO-copolymer PSS was prepared by reduction of PSS. rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were weighed at a mass ratio of 1:0.23:0.45:0.004. 0.2 wt% of rGO-copolymer PSS was added to deionized water, and the mixture was sonicated for 20 min to obtain an rGO-copolymer PSS dispersion. Under a nitrogen atmosphere, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially to the rGO-copolymer PSS dispersion. The mixture was stirred at 25°C and 500 rpm for 20 h, dialyzed against deionized water for 3 days, and freeze-dried to obtain PEDOT:rGO-copolymer PSS. 1.4 wt% of PEDOT:rGO-copolymer PSS was added to deionized water, and the mixture was stirred at 25°C and 500 rpm for 20 min to obtain a coating solution. (2) Hydrogen peroxide and ammonium hydroxide were mixed evenly at a volume ratio of 1:2.8, diluted with deionized water to 20 vol%, and stirred at 25°C and 300 r / min for 10 h to obtain a mixed treatment solution; aluminum foil was immersed in the mixed treatment solution and stirred at 25°C and 300 r / min for 50 min, then washed with ethanol and deionized water and dried to obtain hydroxylated aluminum foil; γ-aminoethylaminopropyltrimethoxysilane was dissolved in dichloromethane to prepare a 0.04 M silane modification solution; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 25°C and 300 r / min for 70 h, washed with deionized water and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, treated at 175°C for 1.5 h in a nitrogen atmosphere, and freeze-dried to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:95:50, stir at 125~135℃ and 300r / min for 1.5h, cool, add terephthalic acid and aerogel-coated aluminum foil with a mass of 1 times that of zirconium propoxide solution, stir at 25℃ for 15h, wash with acetone, and vacuum dry to obtain MOF / aerogel-coated aluminum foil; dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 0.7wt%, add MOF / aerogel-coated aluminum foil, stir at 25℃ for 15h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0022] Example 2: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) In a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed in a mass ratio of 1:0.03:8.8:17.5:100 and stirred at 27°C and 400 r / min for 48 h. The mixture was filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator. In a nitrogen atmosphere, graphene oxide initiator, sodium p-styrenesulfonate, (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine and ethanol / water mixed solvent (V / V=1:1) were mixed in a mass ratio of 1:2.4:0.6:0.065:200. Copper bromide with a mass of 0.045 of graphene oxide initiator was added and stirred at 45°C and 600 r / min for 12 h. The mixture was dialyzed with deionized water for 4 days and freeze-dried to obtain GO-copolymer PSS. rGO-copolymer PSS was prepared by reduction of PSS. rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were weighed in a mass ratio of 1:0.25:0.5:0.0045. 0.25 wt% of rGO-copolymer PSS was added to deionized water, and the mixture was sonicated for 30 min to obtain an rGO-copolymer PSS dispersion. Under a nitrogen atmosphere, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially to the rGO-copolymer PSS dispersion. The mixture was stirred at 27°C and 600 r / min for 24 h, dialyzed against deionized water for 4 days, and freeze-dried to obtain PEDOT:rGO-copolymer PSS. 1.6 wt% of PEDOT:rGO-copolymer PSS was added to deionized water, and the mixture was stirred at 30°C and 600 r / min for 30 min to obtain a coating solution. (2) Hydrogen peroxide and ammonium hydroxide were mixed evenly at a volume ratio of 1:3, diluted with deionized water to 20 vol%, and stirred at 27°C and 400 r / min for 12 h to obtain a mixed treatment solution; aluminum foil was immersed in the mixed treatment solution and stirred at 27°C and 400 r / min for 60 min, then washed with ethanol and deionized water and dried to obtain hydroxylated aluminum foil; γ-aminoethylaminopropyltrimethoxysilane was dissolved in dichloromethane to prepare a 0.045 M silane modification solution; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 27°C and 400 r / min for 72 h, washed with deionized water and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, treated at 180°C for 2 h in a nitrogen atmosphere, and freeze-dried to obtain aerogel-coated aluminum foil; (3) A zirconium propoxide solution, N,N-dimethylformamide and acetic acid were mixed at a mass ratio of 1:97:55 and stirred at 130°C and 400 r / min for 2 h. After cooling, 1.25 times the mass of the zirconium propoxide solution was added to terephthalic acid and aerogel-coated aluminum foil. Stirring was continued at 27°C for 18 h. The mixture was washed with acetone and dried under vacuum to obtain MOF / aerogel-coated aluminum foil. Manganese acetate tetrahydrate was dissolved in N,N-dimethylformamide at 0.85 wt%, and added to MOF / aerogel-coated aluminum foil. Stirring was continued at 27°C for 18 h. The mixture was washed with acetone and dried under vacuum to obtain flexible composite capacitor electrode material.

[0023] Example 3: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed in a mass ratio of 1:0.04:9:18:105, stirred at 30°C and 500 r / min for 50 h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator, sodium p-styrenesulfonate, (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine and ethanol / water mixed solvent (V / V=1:1) were mixed in a mass ratio of 1:2.6:0.7:0.07:205, and 0.05% copper bromide of graphene oxide initiator were added, stirred at 50°C and 700 r / min for 14 h, dialyzed with deionized water for 4 days, and freeze-dried to obtain GO-copolymer PSS; GO-copolymer PSS was prepared by mixing graphene oxide initiator with dichloromethane, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform. rGO-copolymer PSS was prepared by reduction of polyPSS. rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were weighed at a mass ratio of 1:0.27:0.55:0.005. 0.3 wt% of rGO-copolymer PSS was added to deionized water, and the mixture was sonicated for 40 min to obtain an rGO-copolymer PSS dispersion. Under a nitrogen atmosphere, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially to the rGO-copolymer PSS dispersion. The mixture was stirred at 30℃ and 700 rpm for 28 h, dialyzed against deionized water for 4 days, and freeze-dried to obtain PEDOT:rGO-copolymer PSS. 1.8 wt% of PEDOT:rGO-copolymer PSS was added to deionized water, and the mixture was stirred at 35℃ and 700 rpm for 40 min to obtain a coating solution. (2) Hydrogen peroxide and ammonium hydroxide were mixed evenly at a volume ratio of 1:3.2, diluted with deionized water to 20 vol%, and stirred at 30°C and 500 r / min for 14 h to obtain a mixed treatment solution; aluminum foil was immersed in the mixed treatment solution and stirred at 30°C and 500 r / min for 70 min, then washed with ethanol and deionized water and dried to obtain hydroxylated aluminum foil; γ-aminoethylaminopropyltrimethoxysilane was dissolved in dichloromethane to prepare a 0.05 M silane modification solution; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 30°C and 500 r / min for 75 h, washed with deionized water and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, treated at 185°C for 2.5 h in a nitrogen atmosphere, and freeze-dried to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:100:60, stir at 135℃ and 500r / min for 2.5h, cool, add 1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil, stir at 30℃ for 20h, wash with acetone, and vacuum dry to obtain MOF / aerogel-coated aluminum foil; dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 1wt%, add MOF / aerogel-coated aluminum foil, stir at 30℃ for 20h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0024] Comparative Example 1: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) In a nitrogen atmosphere, sodium p-styrene sulfonate, (4-vinylphenyl)methylamine hydrochloride, azobisisobutyronitrile and deionized water were mixed in a mass ratio of 1:0.25:0.125:12.5 and stirred at 70℃ and 600 r / min for 18 h. Methanol was precipitated and the mixture was dried under vacuum to obtain copolymer PSS. Copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate and ferrous sulfate heptahydrate were weighed in a mass ratio of 1:0.25:0.5:0.0045. Copolymer PSS was dissolved in deionized water at 0.25 wt%. Under a nitrogen atmosphere, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially. The mixture was stirred at 27 °C and 600 r / min for 24 h, dialyzed against deionized water for 4 days, and freeze-dried to obtain PEDOT:copolymer PSS. PEDOT:copolymer PSS was added to deionized water at 1.6 wt%, and stirred at 30 °C and 600 r / min for 30 min to obtain a coating solution. (2) Hydrogen peroxide and ammonium hydroxide were mixed evenly at a volume ratio of 1:3, diluted with deionized water to 20 vol%, and stirred at 27°C and 400 r / min for 12 h to obtain a mixed treatment solution; aluminum foil was immersed in the mixed treatment solution and stirred at 27°C and 400 r / min for 60 min, then washed with ethanol and deionized water and dried to obtain hydroxylated aluminum foil; γ-aminoethylaminopropyltrimethoxysilane was dissolved in dichloromethane to prepare a 0.045 M silane modification solution; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 27°C and 400 r / min for 72 h, washed with deionized water and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, treated at 180°C for 2 h in a nitrogen atmosphere, and freeze-dried to obtain aerogel-coated aluminum foil; (3) A zirconium propoxide solution, N,N-dimethylformamide and acetic acid were mixed at a mass ratio of 1:97:55 and stirred at 130°C and 400 r / min for 2 h. After cooling, 1.25 times the mass of the zirconium propoxide solution was added to terephthalic acid and aerogel-coated aluminum foil. Stirring was continued at 27°C for 18 h. The mixture was washed with acetone and dried under vacuum to obtain MOF / aerogel-coated aluminum foil. Manganese acetate tetrahydrate was dissolved in N,N-dimethylformamide at 0.85 wt%, and added to MOF / aerogel-coated aluminum foil. Stirring was continued at 27°C for 18 h. The mixture was washed with acetone and dried under vacuum to obtain flexible composite capacitor electrode material.

[0025] Comparative Example 2: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed at a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105), stirred at 25~30℃ and 300~500r / min for 40~50h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide was... Initiator, sodium p-styrene sulfonate, tris(2-dimethylaminoethyl)amine, and ethanol / water mixed solvent (V / V=1:1) were mixed at a mass ratio of 1:(2.8~3.2):(0.06~0.07):(195~205). Copper bromide with a mass of 0.04~0.05 of the graphene oxide initiator was added. The mixture was stirred at 40~50℃ and 500~700 r / min for 10~14 h, dialyzed against deionized water for 3~4 days, and freeze-dried to obtain GO-PSS. rGO-PSS was prepared by reduction of 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate by mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005). rGO-PSS, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were weighed. rGO-PSS was added to deionized water at 0.2wt%~0.3wt%, and the mixture was sonicated for 20~40 min to obtain an rGO-PSS dispersion. The mixture was then dissolved in nitrogen. 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially to the powder, and the mixture was stirred at 25-30℃ and 500-700 r / min for 20-28 h. After dialyzing with deionized water for 3-4 days, the mixture was freeze-dried to obtain PEDOT:rGO-PSS. PEDOT:rGO-PSS was added to deionized water at 1.4wt%-1.8wt% and stirred at 25-35℃ and 500-700 r / min for 20-40 min to obtain the coating solution. (2) Hydrogen peroxide and ammonium hydroxide are mixed evenly at a volume ratio of 1:(2.8~3.2), diluted with deionized water to 20 vol%, and stirred at 25~30℃ and 300~500 r / min for 10~14 h to obtain a mixed treatment solution; aluminum foil is immersed in the mixed treatment solution and stirred at 25~30℃ and 300~500 r / min for 50~70 min, then removed, washed with ethanol and deionized water, and dried to obtain hydroxylated aluminum foil; γ- A 0.04-0.05M silane modification solution was prepared by dissolving aminoethylaminopropyltrimethoxysilane in dichloromethane; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 25-30℃ and 300-500 r / min for 70-75 h, washed with deionized water, and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, and treated at 175-185℃ for 1.5-2.5 h in a nitrogen atmosphere, followed by freeze-drying to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:(95~100):(50~60), stir at 125~135℃ and 300~500r / min for 1.5~2.5h, cool, add 1~1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain MOF / aerogel-coated aluminum foil; dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 0.7wt%~1wt%, add MOF / aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0026] Comparative Example 3: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed at a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105), stirred at 25~30℃ and 300~500r / min for 40~50h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator and sodium p-styrene sulfonate were mixed. (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine, and an ethanol / water mixture (V / V=1:1) were mixed in a mass ratio of 1:(2.2~2.6):(0.5~0.7):(0.06~0.07):(195~205). Copper bromide (0.04~0.05 by mass of graphene oxide initiator) was added, and the mixture was stirred at 40~50℃ and 500~700 r / min for 10~14 h. After dialyzing with deionized water for 3~4 days, the mixture was freeze-dried to obtain GO-copolymer PS. S; reduce GO-copolymer PSS to obtain rGO-copolymer PSS; weigh rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate and ferrous sulfate heptahydrate at a mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005), add rGO-copolymer PSS to deionized water at 0.2wt%~0.3wt%, and sonicate for 20~40 min to obtain rGO-copolymer PSS dispersion; under a nitrogen atmosphere, add rGO... - The copolymer PSS dispersion was sequentially added with 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate, and stirred at 25-30℃ and 500-700 r / min for 20-28 h. After dialyzing with deionized water for 3-4 days, the mixture was freeze-dried to obtain PEDOT:rGO-copolymer PSS. The PEDOT:rGO-copolymer PSS was added at 1.4wt%-1.8wt% to deionized water and stirred at 25-35℃ and 500-700 r / min for 20-40 min to obtain the coating solution. (2) Spin-coating the coating solution onto the surface of the aluminum foil, treating it at 175~185℃ for 1.5~2.5h in a nitrogen atmosphere, and freeze-drying it to obtain the aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:(95~100):(50~60), stir at 125~135℃ and 300~500r / min for 1.5~2.5h, cool, add 1~1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain MOF / aerogel-coated aluminum foil; dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 0.7wt%~1wt%, add MOF / aerogel-coated aluminum foil, continue stirring at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0027] Comparative Example 4: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed at a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105), stirred at 25~30℃ and 300~500r / min for 40~50h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator and sodium p-styrene sulfonate were mixed. (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine, and an ethanol / water mixture (V / V=1:1) were mixed in a mass ratio of 1:(2.2~2.6):(0.5~0.7):(0.06~0.07):(195~205). Copper bromide (0.04~0.05 by mass of graphene oxide initiator) was added, and the mixture was stirred at 40~50℃ and 500~700 r / min for 10~14 h. After dialyzing with deionized water for 3~4 days, the mixture was freeze-dried to obtain GO-copolymer PS. S; reduce GO-copolymer PSS to obtain rGO-copolymer PSS; weigh rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate and ferrous sulfate heptahydrate at a mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005), add rGO-copolymer PSS to deionized water at 0.2wt%~0.3wt%, and sonicate for 20~40 min to obtain rGO-copolymer PSS dispersion; under a nitrogen atmosphere, add rGO... - The copolymer PSS dispersion was sequentially added with 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate, and stirred at 25-30℃ and 500-700 r / min for 20-28 h. After dialyzing with deionized water for 3-4 days, the mixture was freeze-dried to obtain PEDOT:rGO-copolymer PSS. The PEDOT:rGO-copolymer PSS was added at 1.4wt%-1.8wt% to deionized water and stirred at 25-35℃ and 500-700 r / min for 20-40 min to obtain the coating solution. (2) Hydrogen peroxide and ammonium hydroxide are mixed evenly at a volume ratio of 1:(2.8~3.2), diluted with deionized water to 20 vol%, and stirred at 25~30℃ and 300~500 r / min for 10~14 h to obtain a mixed treatment solution; aluminum foil is immersed in the mixed treatment solution and stirred at 25~30℃ and 300~500 r / min for 50~70 min, then removed, washed with ethanol and deionized water, and dried to obtain hydroxylated aluminum foil; γ- A 0.04-0.05M silane modification solution was prepared by dissolving aminoethylaminopropyltrimethoxysilane in dichloromethane; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 25-30℃ and 300-500 r / min for 70-75 h, washed with deionized water, and dried to obtain modified aluminum foil; the coating solution was spin-coated onto the surface of the modified aluminum foil, and treated at 175-185℃ for 1.5-2.5 h in a nitrogen atmosphere, followed by freeze-drying to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:(95~100):(50~60), stir at 125~135℃ and 300~500r / min for 1.5~2.5h, cool, add 1~1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil, stir at 25~30℃ for 15~20h, wash with acetone, and vacuum dry to obtain flexible composite capacitor electrode material.

[0028] Comparative Example 5: A method for preparing a flexible composite capacitor electrode material includes the following preparation steps: (1) Under a nitrogen atmosphere, graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform were mixed at a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105), stirred at 25~30℃ and 300~500r / min for 40~50h, filtered, washed with dichloromethane and methanol, and dried to obtain graphene oxide initiator; under a nitrogen atmosphere, graphene oxide initiator and sodium p-styrene sulfonate were mixed. (4-vinylphenyl)methylamine hydrochloride, tris(2-dimethylaminoethyl)amine, and an ethanol / water mixture (V / V=1:1) were mixed in a mass ratio of 1:(2.2~2.6):(0.5~0.7):(0.06~0.07):(195~205). Copper bromide (0.04~0.05 by mass of graphene oxide initiator) was added, and the mixture was stirred at 40~50℃ and 500~700 r / min for 10~14 h. After dialyzing with deionized water for 3~4 days, the mixture was freeze-dried to obtain GO-copolymer PS. S; reduce GO-copolymer PSS to obtain rGO-copolymer PSS; weigh rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate and ferrous sulfate heptahydrate at a mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005), add rGO-copolymer PSS to deionized water at 0.2wt%~0.3wt%, and sonicate for 20~40 min to obtain rGO-copolymer PSS dispersion; under a nitrogen atmosphere, add rGO... - The copolymer PSS dispersion was sequentially added with 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate, and stirred at 25-30℃ and 500-700 r / min for 20-28 h. After dialyzing with deionized water for 3-4 days, the mixture was freeze-dried to obtain PEDOT:rGO-copolymer PSS. The PEDOT:rGO-copolymer PSS was added at 1.4wt%-1.8wt% to deionized water and stirred at 25-35℃ and 500-700 r / min for 20-40 min to obtain the coating solution. (2) Hydrogen peroxide and ammonium hydroxide are mixed evenly at a volume ratio of 1:(2.8~3.2), diluted with deionized water to 20 vol%, and stirred at 25~30℃ and 300~500 r / min for 10~14 h to obtain a mixed treatment solution; aluminum foil is immersed in the mixed treatment solution and stirred at 25~30℃ and 300~500 r / min for 50~70 min, then removed, washed with ethanol and deionized water, and dried to obtain hydroxylated aluminum foil; γ-aminoethyl A 0.04-0.05M silane modification solution was prepared by dissolving aminopropyltrimethoxysilane in dichloromethane; hydroxylated aluminum foil was immersed in the silane modification solution and stirred at 25-30℃ and 300-500 r / min for 70-75 h, washed with deionized water, and dried to obtain modified aluminum foil; a coating solution was spin-coated onto the surface of the modified aluminum foil, and the foil was treated at 175-185℃ for 1.5-2.5 h in a nitrogen atmosphere and freeze-dried to obtain a flexible composite capacitor electrode material.

[0029] Experimental Example 1: This example tests the performance of the flexible composite capacitor electrode materials obtained in Examples 1-3 and Comparative Examples 1-5. The specific test items and methods are as follows: Conductivity testing method: The flexible composite capacitor electrode materials obtained in each embodiment and the materials of comparative examples 1 to 5 are cut into pieces with a size of 1 cm. 2 A square with a thickness of 1.5 mm was tested using the four-probe method.

[0030] Specific capacitance testing and calculation method: The specific capacitance was calculated by constant current charge-discharge test. The flexible composite capacitor electrode materials obtained in each embodiment and the materials of comparative examples 1 to 5 were used as working electrodes, and they were cut to 1 cm in size during the test. 2 The square shape, with the counter electrode being 1cm. 2 The electrode used is a platinum electrode, the reference electrode is a calomel electrode, the liquid electrolyte is a 1M potassium hydroxide solution, and the current density is 0.2 mA / cm². 2 .

[0031] Electrode material specific capacitance (F / cm) 2 = (I×∆t) / (S×∆V) I is the current (A); ∆t is the discharge time (s); S is the area of ​​the electrode material (cm²). 2 ); ∆V is the voltage difference (V) after the IR drop.

[0032] Charge-discharge cycle capacitance retention rate test and calculation method: The specific capacitance is calculated by constant current charge-discharge test. The flexible composite capacitor electrode materials obtained in each embodiment and the materials of comparative examples 1 to 5 are used as working electrodes. During the test, they are cut to 1 cm. 2 The square shape, with the counter electrode being 1cm. 2The platinum electrode was used, while the reference electrode was a calomel electrode. The liquid electrolyte was a 1M potassium hydroxide solution. The cyclic test was set to 2000 cycles, with a voltage range of 0~0.5V and a current density of 5mA / cm². 2 .

[0033] Charge-discharge cycle capacitance retention rate = (C N / C1)×100% C N C1 is the discharge capacitance in the Nth cycle; C2 is the discharge capacitance in the 1st cycle.

[0034] Bending cycle specific capacitance retention rate test and calculation method: The flexible composite capacitor electrode materials obtained in each embodiment and the materials of comparative examples 1 to 5 are used as positive and negative electrodes, and polyvinyl alcohol-potassium hydroxide is used as solid electrolyte to assemble a flexible all-solid-state supercapacitor. One end of the capacitor is connected to the working electrode clamp, and the other end is connected to the auxiliary electrode clamp and the reference electrode clamp. The initial specific capacitance is calculated by constant current charge and discharge test. Then, the flexible all-solid-state supercapacitor is bent at 90° 500 times, and constant current charge and discharge test is performed again to calculate the specific capacitance value and the bending cycle specific capacitance retention rate.

[0035] The results are shown in Table 1.

[0036] Table 1 Electrical conductivity (S / cm) <![CDATA[Specific capacitance (mF / cm 2 )]]> Charge-discharge cycle capacitance retention (%) Bending cycle specific capacitance retention (%) Example 1 1.57 1627 95.9% 96.5% Example 2 1.61 1632 96.3% 96.8% Example 3 1.59 1630 96.1% 96.3% Comparative Example 1 1.13 1038 92.3% 82.8% Comparative Example 2 1.37 1614 95.8% 96.2% Comparative Example 3 1.57 1626 81.2% 70.3% Comparative Example 4 1.59 1451 95.1% 95.2% Comparative Example 5 1.66 1323 96.3% 96.7% A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-5 in Table 1 reveals that the flexible composite capacitor electrode material prepared by this invention exhibits good flexibility, high specific capacitance, and cycle stability.

[0037] A comparison of Examples 1-3 and Comparative Example 1 reveals that the addition of graphene oxide as an atom transfer radical polymerization initiator not only provides a high specific surface area supporting substrate, but also ensures that the PSS copolymer grows regularly in a "grafting" manner through its surface initiation sites, thereby forming a tightly interconnected "conductive interpenetrating network" with the subsequent PEDOT. Comparative Example 1, using AIBN for homogeneous radical polymerization, produced a PSS copolymer that was a random coil, lacking an ordered conductive scaffold. This resulted in a decrease in the material's electrical conductivity and specific capacitance based on rapid ion response, as well as compromised mechanical integrity and deteriorated cycle and bending stability.

[0038] By comparing Examples 1-3 and Comparative Example 2, it can be found that the introduction of (4-vinylphenyl)methylamine hydrochloride monomer during the copolymerization process results in stronger hydrogen bonding and electrostatic interactions between its amino functional groups and other components in the system. This promotes the formation of a more stable and cross-linked three-dimensional gel network, improves the uniformity and density of the PEDOT:rGO coating, reduces structural defects, and enhances the structural integrity and electrochemical stability of the material during repeated charge and discharge processes.

[0039] A comparison of Examples 1-3 and Comparative Example 3 reveals that hydroxylation and silane coupling agent modification of the aluminum foil play a crucial role in constructing a strong and robust chemical covalent bond bridge between the metal substrate and the organic coating. Hydroxylation creates abundant -Al-OH active sites, which are then firmly bonded to the silane via Si-O-Al bonds after hydrolysis. The amino groups at the other end of the silane interact electrostatically or through hydrogen bonding with the functional groups in the coating. This process transforms physical adsorption into chemical bonding. Comparative Example 3 uses smooth commercial aluminum foil, where the coating adheres only by weak van der Waals forces. Under the stress of ion insertion / extraction during charge / discharge and the mechanical stress of repeated bending, the coating is easily detached, resulting in a sharp decrease in cycle stability, especially the bending cycle retention rate.

[0040] A comparison of Examples 1-3 and Comparative Example 4 reveals that the introduction of manganese acetate tetrahydrate during MOF preparation has several advantages. Firstly, the released manganese ions act as redox active centers, contributing significantly to pseudocapacitance and directly determining high capacity. Secondly, manganese ions can form coordination bonds with functional groups in the MOF organic ligands and coating polymer network, enhancing internal crosslinking density and interfacial ionic bonding, thereby improving the overall structural integrity of the coating during electrochemical cycling.

[0041] A comparison of Examples 1-3 and Comparative Example 5 reveals that the introduction of the MOF coating significantly increases the effective specific surface area of ​​the electrode material and introduces a large number of pseudocapacitive active sites. The MOF acts like a sponge with molecular-level pores and a high surface area, "grown" on the conductive aerogel framework, greatly increasing the number of interfaces accessible to the electrolyte and the number of manganese active centers. Comparative Example 5 completely lacks this structure, resulting in a significant decrease in areal capacitance.

[0042] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and not restrictive.

Claims

1. A flexible composite capacitor electrode material, characterized in that, The flexible composite capacitor electrode material comprises a modified aluminum foil with a PEDOT:rGO-copolymer PSS composite aerogel coating and a zirconium-based metal-organic framework (MOF) having manganese ion active sites, which are sequentially coated and grown on the surface.

2. The flexible composite capacitor electrode material according to claim 1, characterized in that, The PEDOT:rGO-copolymer PSS composite aerogel coating is prepared by brominating graphene oxide to obtain graphene oxide initiator, reacting it with sodium p-styrene sulfonate and (4-vinylphenyl)methylamine hydrochloride and reducing it to obtain rGO-copolymer PSS, and then polymerizing it with 3,4-ethylenedioxythiophene.

3. The flexible composite capacitor electrode material according to claim 1, characterized in that, The zirconium-based metal-organic framework with manganese ion active sites is prepared by growing the zirconium-based metal-organic framework in aerogel pores and complexing manganese ions.

4. The flexible composite capacitor electrode material according to claim 1, characterized in that, The modified aluminum foil is prepared by treating aluminum foil with hydrogen peroxide and ammonium hydroxide and then modifying it with silane.

5. A method for preparing a flexible composite capacitor electrode material, characterized in that, The preparation steps include the following: (1) A solution of graphene oxide, 4-dimethylaminopyridine, triethylamine, 2-bromoisobutyryl bromide in dichloromethane and anhydrous chloroform in a mass ratio of 1:(0.02~0.04):(8.5~9):(17~18):(95~105) was mixed and reacted at 25~30℃ for 40~50h to obtain a graphene oxide initiator; the graphene oxide initiator, sodium p-styrenesulfonate, and (4-vinylphenyl)methylamine salt were then mixed. A GO-copolymer PSS was prepared by mixing a salt, tris(2-dimethylaminoethyl)amine, and an ethanol / water mixed solvent (V / V = 1:1) at a mass ratio of 1:(2.2~2.6):(0.5~0.7):(0.06~0.07):(195~205), adding 0.04~0.05% copper bromide as a graphene oxide initiator, and reacting at 40~50℃ for 10~14 h. rGO-copolymer PSS was prepared by reduction. rGO-copolymer PSS, 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were weighed at a mass ratio of 1:(0.23~0.27):(0.45~0.55):(0.004~0.005). 0.2wt%~0.3wt% of rGO-copolymer PSS was added to deionized water, and the mixture was sonicated for 20~40 min to obtain an rGO-copolymer PSS dispersion. 3,4-ethylenedioxythiophene, sodium persulfate, and ferrous sulfate heptahydrate were added sequentially to the rGO-copolymer PSS dispersion, and the mixture was reacted at 25~30℃ for 20~28 h to obtain PEDOT:rGO-copolymer PSS. 1.4wt%~1.8wt% of PEDOT:rGO-copolymer PSS was added to deionized water, and the mixture was stirred at 25~35℃ for 20~40 min to obtain a coating solution. (2) Hydrogen peroxide and ammonium hydroxide are mixed evenly at a volume ratio of 1:(2.8~3.2), diluted with deionized water to 20 vol%, and reacted at 25~30℃ for 10~14 h to obtain a mixed treatment solution; aluminum foil is immersed in the mixed treatment solution and treated at 25~30℃ for 50~70 min to obtain hydroxylated aluminum foil; γ-aminoethylaminopropyltrimethoxysilane is dissolved in dichloromethane to prepare a 0.04~0.05M silane modification solution; Hydroxylated aluminum foil was immersed in a silane modification solution and treated at 25-30°C for 70-75 hours to obtain modified aluminum foil. The coating solution was spin-coated onto the surface of the modified aluminum foil and treated at 175~185℃ for 1.5~2.5h to obtain aerogel-coated aluminum foil; (3) Mix zirconium propoxide solution, N,N-dimethylformamide and acetic acid at a mass ratio of 1:(95~100):(50~60) and react at 125~135℃ for 1.5~2.5h. After cooling, add 1~1.5 times the mass of zirconium propoxide solution of terephthalic acid and aerogel-coated aluminum foil and continue to react at 25~30℃ for 15~20h to obtain MOF / aerogel-coated aluminum foil. Dissolve manganese acetate tetrahydrate in N,N-dimethylformamide at 0.7wt%~1wt%, add MOF / aerogel-coated aluminum foil, and continue to react at 25~30℃ for 15~20h to obtain flexible composite capacitor electrode material.

6. The method for preparing a flexible composite capacitor electrode material according to claim 5, characterized in that, The graphene oxide in step (1) has a thickness of ≤5nm and a sheet diameter of 10μm.

7. The method for preparing a flexible composite capacitor electrode material according to claim 5, characterized in that, The specific method for reducing GO-copolymer PSS to obtain rGO-copolymer PSS in step (1) is as follows: Under nitrogen protection, GO-copolymer PSS is uniformly dispersed in deionized water at a concentration of 0.5~1.0 mg / mL, ultrasonically treated for 30 min, ascorbic acid with a mass of 7~9 times that of GO-copolymer PSS is added, and the mixture is stirred at 70~80℃ and 300~500 r / min for 4~6 h, washed with deionized water, and dried to obtain rGO-copolymer PSS.

8. The method for preparing a flexible composite capacitor electrode material according to claim 5, characterized in that, The aluminum foil in step (2) is a commercial aluminum foil with a thickness of 0.03 mm.

9. The method for preparing a flexible composite capacitor electrode material according to claim 5, characterized in that, The specific method of spin coating in step (2) is as follows: the coating solution is dripped onto the modified aluminum foil with a syringe to form a film with an initial thickness of about 0.3 mm, and then rotated at 800~900 r / min for 15 s.

10. The method for preparing a flexible composite capacitor electrode material according to claim 5, characterized in that, The zirconium propoxide solution in step (3) has a mass percentage of 70 wt%.