Method for preparing dissolving pulp / carbon conductive material / polypyrrole composite membrane material from lithium bromide solution and application of dissolving pulp / carbon conductive material / polypyrrole composite membrane material
By using lithium bromide solution to dissolve the dissolving slurry and mix it with carbon conductive material, and polymerizing polypyrrole in the cellulose electrode, the problem of poor mechanical properties of the electrode in the prior art is solved, and a high-performance, self-supported supercapacitor electrode is achieved.
Patent Information
- Application Number
- CN202510229546.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-28
- Publication Date
- 2025-05-06
AI Technical Summary
In the prior art, the mechanical properties of directly preparing electrodes using carbon conductive materials are poor, and the cellulose material itself does not have electrical conductivity. Directly coated carbon conductive materials cannot be used as electrodes. It is usually necessary to carbonize the cellulose and then composite it with the conductive material, resulting in a decrease in mechanical properties.
The lithium bromide solution is used to dissolve the dissolution slurry, mix it with carbon conductive material carbon nanotubes and reduced graphene oxide to form a uniform mixture of cellulose and carbon conductive material, and polymerize polypyrroles internally to prepare high-performance supercapacitor electrodes.
By forming a three-dimensional pore structure and conductive pathway, electrochemical performance is improved, and a self-supported supercapacitor electrode is realized without the need for cellulose carbonized, avoiding the reduction of mechanical properties.
Smart Images
Figure CN119943585A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of capacitor electrode materials, and specifically relates to a method for preparing a dissolving slurry / carbon conductive material / polypyrrole composite film material from a lithium bromide solution and application thereof. Background Art
[0002] The information disclosed in the background of the invention is only intended to enhance the understanding of the overall background of the invention and should not be necessarily regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.
[0003] Cellulose is the most abundant natural renewable polymer on earth so far. It comes from various plants, and commercial cellulose products usually come from wood and cotton. Cellulose raw materials come in various forms and types, including microcrystalline cellulose, nanocellulose (including nanocellulose fibrils and nanocellulose crystals), and various water-soluble cellulose derivatives. They are green, sustainable, high in strength and stiffness, lightweight, biodegradable and renewable.
[0004] Cellulose can be used to prepare materials with porous structures and conductive channels. Due to its excellent network and pore structure, as well as rich functional groups, it can be used in supercapacitor components (including electrodes, electrolytes and diaphragm materials). Electrodes prepared from cellulose materials not only have high capacitance, rate performance, energy density, power density and long cycle period, but also can achieve excellent performance and thermal stability in a wide temperature range. Natural polysaccharide cellulose and its derivatives have high aspect ratio, high specific surface area, high porosity, excellent mechanical properties and excellent flexibility, and are very promising substrate materials for the preparation of high-performance supercapacitor electrodes.
[0005] The open channels of the rich 3D structure of cellulose-based materials can absorb electrolytes to the greatest extent, and the adjustable pore structure and specific surface area can provide greater room for improving energy density and power density. At the same time, the high Young's modulus, mechanical strength and micron-scale size of cellulose are very beneficial for obtaining high-strength materials and improving energy transfer efficiency. A large number of groups on the surface of cellulose can adsorb different ions, which is conducive to their shuttling between them. Due to the limited conductivity of cellulose itself, carbon materials such as carbon nanotubes, graphene, conductive carbon black and other materials are usually added. Conductive polymers, metal particles and the like can also be used to increase conductivity. Methods for preparing supercapacitor electrodes with cellulose include introducing conductive materials to prepare cellulose composite aerogel electrodes; depositing conductive substances to prepare cellulose-based electrodes; and carbonizing cellulose to prepare carbon-based electrodes.
[0006] In the prior art, the mechanical properties of electrodes directly prepared with carbon conductive materials are poor, and they are usually coated on metal current collectors such as copper foil, aluminum foil or nickel foam. In recent years, there have been many studies on the use of cellulose, a rich and degradable biomass material, as an electrode component. Since cellulose materials themselves are not conductive, they cannot be used as electrodes if they are directly coated with carbon conductive materials. The usual practice is to carbonize cellulose and then composite it with conductive materials, but this will reduce the mechanical properties of cellulose. Therefore, it is urgent for those skilled in the art to explore a technical solution for preparing self-supporting supercapacitor electrodes by using cellulose materials without carbonization and directly combining them with carbon conductive materials to build a network structure. Summary of the invention
[0007] In view of the needs of the prior art, the purpose of the present invention is to provide a method and application of preparing a dissolving pulp / carbon conductive material / polypyrrole composite membrane material using a lithium bromide solution. The present invention uses a lithium bromide aqueous solution to dissolve the dissolving pulp, mixes it with conductive materials carbon nanotubes and reduced graphene oxide to prepare a membrane material, and polymerizes polypyrrole inside to prepare a high-performance supercapacitor electrode. Specifically, the lithium bromide aqueous solution can fully dissolve the dissolving pulp to form a uniform cellulose solution, and the carbon conductive material is dispersed in the cellulose solution to form a uniform mixture of cellulose and carbon conductive materials. The membrane obtained after regeneration has an open micron-sized pore channel and a clear pore structure is formed inside. The cellulose has a good dispersing effect on the two carbon conductive materials. The porous network structure formed is conducive to the transmission and rapid diffusion of electrolyte ions. The carbon conductive material provides a double-layer capacitor. In order to further improve the electrochemical performance of the material, a simple soaking-polymerization method is used to polymerize the conductive polymer polypyrrole with a high theoretical pseudocapacitance in the above material to obtain a high-performance electrode material.
[0008] Specifically, the present invention provides the following technical solutions: In a first aspect of the present invention, a method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material from a lithium bromide solution is provided, comprising the following steps: S1, adding the dissolving pulp into a lithium bromide aqueous solution to carry out a dissolution reaction to obtain a cellulose solution; S2, adding the carbon conductive material into the cellulose solution for dispersion to obtain a dissolving pulp / carbon conductive material film; S3, soaking the dissolving slurry / carbon conductive material film in a mixed solution containing pyrrole monomer and dopant, and then adding it into an oxidant solution to carry out polymerization reaction, so as to obtain a dissolving slurry / carbon conductive material / polypyrrole composite film material.
[0009] Preferably, in step S1, the molar ratio of lithium bromide to water in the lithium bromide aqueous solution is 1:3-3.5.
[0010] Preferably, in step S1, the degree of polymerization of the dissolving pulp is 500-900, and the α-cellulose content is greater than 91%; the mass fraction of the dissolving pulp is 0.3-1.0%, the temperature of the dissolution reaction is 120-130°C, the dissolution time is 15-30 min, and the stirring rate is 800-1200 rmp.
[0011] Preferably, in step S2, the carbon conductive material is a compound of carbon nanotubes and reduced graphene oxide, and the mass ratio of the carbon nanotubes, reduced graphene oxide and dissolving pulp is 1:1:1.
[0012] Preferably, in step S2, the dispersion time is 30 to 60 min, and the membrane material obtained after the dispersion is washed to neutrality and dried to obtain a dissolving slurry / carbon conductive material membrane.
[0013] Preferably, in step S3, the dopant is selected from one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sodium p-toluenesulfonate, benzenesulfonic acid, and naphthalenesulfonic acid.
[0014] Preferably, in step S3, the concentration of the pyrrole monomer is 0.5-1.0 mol / L; and the molar ratio of the pyrrole monomer to the dopant in the mixed solution is 1:0.5-3.
[0015] Preferably, in step S3, the oxidant is selected from one or more of ferric chloride, vanadium pentoxide, peracetic acid, ammonium persulfate, hydrogen peroxide, and hydrogen peroxide, the concentration of the oxidant solution is 0.75-1.0 mol / L, and the molar ratio of the oxidant to the pyrrole monomer is 1-2:1.
[0016] Preferably, in step S3, the polymerization reaction time is 2 to 8 h.
[0017] The second aspect of the present invention provides a dissolving pulp / carbon conductive material / polypyrrole composite film material, which is prepared by the method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material using a lithium bromide solution as described in the first aspect.
[0018] The third aspect of the present invention provides a membrane electrode, comprising the dissolving slurry / carbon conductive material / polypyrrole composite membrane material described in the second aspect.
[0019] A fourth aspect of the present invention provides a supercapacitor comprising the membrane electrode described in the third aspect.
[0020] The fifth aspect of the present invention provides a use of the dissolving pulp / carbon conductive material / polypyrrole composite film material described in the second aspect in capacitor energy storage devices and supercapacitor electrode materials.
[0021] The beneficial effects achieved by one or more of the above technical solutions of the present invention are as follows: (1) The present invention provides a method of effectively dissolving a dissolving slurry using a lithium bromide solution to achieve effective dispersion of conductive carbon materials carbon nanotubes and reduced graphene oxide. The formed membrane material has a three-dimensional pore structure and can form a conductive path. By synthesizing polypyrrole inside the membrane, the material has better electrochemical properties.
[0022] (2) The present invention uses cellulose, a biomass material that is biodegradable and widely available, as the electrode support, which is dissolved in lithium bromide solution. The dissolved cellulose can evenly disperse the carbon conductive material, and the spatial network structure of the composite film formed is a good conductive path. At the same time, in order to further improve the electrochemical performance, the composite organic conductive material polypyrrole, the three-dimensional spatial structure constructed by cellulose and carbon conductive material can provide a skeleton for pyrrole polymerization, and obtain a self-supporting supercapacitor electrode with excellent electrochemical performance.
[0023] (3) In the present invention, the membrane material after the polymerization reaction can be directly washed, dried, and pressed into sheets to form a supercapacitor electrode material with excellent electrochemical properties. BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.
[0025] Figure 1 This is a scanning electron microscope image (SEM) of the dissolving pulp / carbon conductive material / polypyrrole composite film material prepared in Example 1 of the present invention; Figure 2 This is a scanning electron microscope image of the dissolving pulp / carbon conductive material / polypyrrole composite film material prepared in Example 3 of the present invention; Figure 3 CV curves of dissolving slurry / carbon conductive material / polypyrrole composite film materials prepared by lithium bromide solutions prepared in Examples 1 to 4 of the present invention at different polymerization times; Figure 4 GCD curves of the dissolving slurry / carbon conductive material / polypyrrole composite film material prepared by the lithium bromide solution prepared in Examples 1 to 4 of the present invention at different polymerization times. DETAILED DESCRIPTION
[0026] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.
[0027] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in conjunction with specific embodiments.
[0028] In the following examples, dissolving pulp was purchased from sappi papier holding GmbH, product model SappiVerve.
[0029] Dissolving pulp is a type of cellulose raw material, which is the product of wood after removing impurities such as lignin and hemicellulose. It is a relatively pure fluff pulp after filtering, mainly used as raw material in light manufacturing, especially chemical fiber manufacturing, and can partially replace fibers such as cotton.
[0030] Example 1 :A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite supercapacitor electrode using a lithium bromide solution system, comprising the following steps: (1) 0.041 g of dissolving pulp with a degree of polymerization of 750 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3, the mass fraction of the dissolving pulp was 0.5%, and the process conditions were: temperature 125 °C, dissolution time 25 min, and stirring speed 800 rmp.
[0031] (2) 0.041 g of carbon nanotubes and 0.041 g of reduced graphene oxide were respectively added to the cellulose solution of (1) to make the two substances evenly dispersed in the system. The process conditions were: time 45 min, temperature 125°C, stirring rate 800 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0032] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide film is washed with deionized water until neutral and vacuum dried.
[0033] (4) Prepare a 1.0 mol / L pyrrole monomer solution, add 8.61 g of p-toluenesulfonic acid to 50 mL of the solution, and soak the membrane obtained in step (3) in the above mixed solution for 2 hours. Then, place it in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 2 hours to obtain a composite electrode material.
[0034] like Figure 1 As shown, the scanning electron microscope image of the composite electrode material prepared in this embodiment shows that after the cellulose is dissolved, RGO and CNT are dispersed in the cellulose solution, and the aerogel obtained after regeneration has an open micron-sized pore channel, a clear pore structure is formed inside, and the cross-sectional surface is very rough with wrinkles and grooves.
[0035] Example 2 :A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite supercapacitor electrode using a lithium bromide solution system, comprising the following steps: (1) 0.041 g of dissolving pulp with a degree of polymerization of 750 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3, the mass fraction of the dissolving pulp was 0.5%, and the process conditions were: temperature 125 °C, dissolution time 25 min, and stirring speed 800 rmp.
[0036] (2) 0.041 g of carbon nanotubes and 0.041 g of reduced graphene oxide were respectively added to the cellulose solution of (1) to make the two substances evenly dispersed in the system. The process conditions were: time 45 min, temperature 125°C, stirring rate 800 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0037] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide film is washed with deionized water until neutral and vacuum dried.
[0038] (4) Prepare a 1.0 mol / L pyrrole monomer solution, add 8.61 g of p-toluenesulfonic acid to 50 mL of the solution, and soak the membrane obtained in step (3) in the mixed solution for 2 hours. Then, place the membrane in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 4 hours to obtain a composite electrode material.
[0039] Example 3 :A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite supercapacitor electrode using a lithium bromide solution system, comprising the following steps: (1) 0.041 g of dissolving pulp with a degree of polymerization of 750 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3, the mass fraction of the dissolving pulp was 0.5%, and the process conditions were: temperature 125 °C, dissolution time 25 min, and stirring speed 800 rmp.
[0040] (2) 0.041 g of carbon nanotubes and 0.041 g of reduced graphene oxide were respectively added to the cellulose solution of (1) to make the two substances evenly dispersed in the system. The process conditions were: time 45 min, temperature 125°C, stirring rate 800 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0041] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide film is washed with deionized water until neutral and vacuum dried.
[0042] (4) Prepare a 1.0 mol / L pyrrole monomer solution, add 8.61 g of p-toluenesulfonic acid to 50 mL of the solution, and soak the membrane obtained in step (3) in the above mixed solution for 2 hours. Then, place it in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 6 hours to obtain a composite electrode material.
[0043] like Figure 2 As shown, the scanning electron microscope image of the composite electrode material prepared in this example shows that CNT and RGO are evenly distributed among the cellulose fibers without obvious aggregation, indicating that cellulose has a good dispersing effect on them. CNT and RGO are evenly dispersed among the fibers to form a porous network structure, which is conducive to the transport and rapid diffusion of electrolyte ions.
[0044] Example 4 :A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite supercapacitor electrode using a lithium bromide solution system, comprising the following steps: (1) 0.041 g of dissolving pulp with a degree of polymerization of 750 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3, the mass fraction of the dissolving pulp was 0.5%, and the process conditions were: temperature 125 °C, dissolution time 25 min, and stirring speed 800 rmp.
[0045] (2) 0.041 g of carbon nanotubes and 0.041 g of reduced graphene oxide were respectively added to the cellulose solution of (1) to make the two substances evenly dispersed in the system. The process conditions were: time 45 min, temperature 125°C, stirring rate 800 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0046] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide film is washed with deionized water until neutral and vacuum dried.
[0047] (4) Prepare a 1.0 mol / L pyrrole monomer solution, add 8.61 g of p-toluenesulfonic acid to 50 mL of the solution, and soak the membrane obtained in step (3) in the above mixed solution for 2 hours. Then, place it in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 8 hours to obtain a composite electrode material.
[0048] Example 5 :This embodiment provides a method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material from a lithium bromide solution, comprising the following steps: (1) 0.082 g of dissolving pulp with a degree of polymerization of 520 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3.5, the mass fraction of the dissolving pulp was 1.0%, and the process conditions were: temperature 120 °C, dissolution time 15 min, and stirring speed 800 rmp.
[0049] (2) 0.082 g of carbon nanotubes and 0.082 g of reduced graphene oxide were respectively added to the cellulose solution in (1) to make the two substances evenly dispersed in the system. The process conditions were: time 30 min, temperature 120°C, stirring rate 1000 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide gel film was formed.
[0050] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide gel film is washed with deionized water until neutral and vacuum dried.
[0051] (4) Prepare a 0.5 mol / L aqueous solution of pyrrole monomer, take 50 mL, add 4.3 g of p-toluenesulfonic acid thereto, the molar ratio of pyrrole monomer to p-toluenesulfonic acid in the mixed solution is 1:1, soak the dried membrane obtained in step (3) in the above mixed solution for 2 hours, then put it into 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 2 hours to obtain a composite electrode material.
[0052] Example 6 :This embodiment provides a method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material using a lithium bromide solution system, comprising the following steps: (1) 0.065 g of dissolving pulp with a degree of polymerization of 700 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3.3, the mass fraction of the dissolving pulp was 0.8%, and the process conditions were: temperature 125 °C, dissolution time 20 min, and stirring speed 800 rmp.
[0053] (2) 0.065 g of carbon nanotubes and 0.065 g of reduced graphene oxide were respectively added to the cellulose solution in (1) to make the two substances evenly dispersed in the system. The process conditions were: time 40 min, temperature 125 °C, stirring rate 800 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0054] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide hydrogel film was washed with deionized water until neutral and dried in vacuum.
[0055] (4) Prepare a 0.6 mol / L pyrrole monomer solution, add 5.166 g of p-toluenesulfonic acid to 50 mL of the solution, and soak the membrane obtained in step (3) in the above mixed solution for 2 hours. Then, place it in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 4 hours to obtain a composite electrode material.
[0056] Example 7 :A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite supercapacitor electrode using a lithium bromide solution system, comprising the following steps: (1) 0.049 g of dissolving pulp with a degree of polymerization of 800 was added to 8.11 g of lithium bromide aqueous solution. The molar ratio of lithium bromide to water was 1:3, the mass fraction of the dissolving pulp was 0.6%, and the process conditions were: temperature 130 °C, dissolution time 30 min, and stirring rate 1000 rmp.
[0057] (2) 0.049 g of carbon nanotubes and 0.049 g of reduced graphene oxide were respectively added to the cellulose solution of (1) to make the two substances evenly dispersed in the system. The process conditions were: time 50 min, temperature 130 °C, stirring rate 1000 rpm. After cooling, a dissolving slurry / carbon nanotubes / reduced graphene oxide hydrogel film was formed.
[0058] (3) The prepared dissolving pulp / carbon nanotube / reduced graphene oxide film is washed with deionized water until neutral and vacuum dried.
[0059] (4) Prepare a 0.7 mol / L pyrrole monomer solution, add 6 g of p-toluenesulfonic acid to 50 mL of the above solution, and soak the membrane obtained in step (3) in the above mixed solution for 2 hours. Then, place it in 50 mL of 0.75 mol / L ferric chloride solution and soak it in an ice bath for 8 hours to obtain a composite electrode material.
[0060] Test Example 1 In this test example, the dissolving slurry / carbon conductive material / polypyrrole composite film material prepared in Examples 1 to 4 was prepared into a membrane electrode, and the electrochemical performance test was carried out.
[0061] Experimental process: The dissolving slurry / carbon conductive material / polypyrrole composite film obtained in step (4) of Examples 1 to 4 was washed, vacuum dried, and pressed into sheets to obtain a working electrode. Then, an Ag / AgCl electrode was used as a reference electrode, a platinum electrode was used as a counter electrode, and 1 mol L -1 Sulfuric acid solution was used as the electrolyte, and three-electrode tests were performed using cyclic voltammetry (CV) and constant current charge and discharge (GCD). The results are as follows: Through CV test, at a scan rate of 5 mV / s, the area specific capacitance of the composite single electrode of the membrane electrode prepared by the dissolving pulp / carbon conductive material / polypyrrole composite membrane material prepared in Examples 1 to 4 was calculated to be 1927.75 mF / cm 2 、1590.5 mF / cm 2 、1239.25 mF / cm 2 、1283.75 mF / cm 2 ,like Figure 3 shown.
[0062] Through GCD test, at a current density of 2 mA / cm 2 By calculation, the area specific capacitance of the membrane electrode prepared by the dissolving pulp / carbon conductive material / polypyrrole composite membrane material prepared in Examples 1 to 4 is 1979.6 mF / cm 2 、1732.9 mF / cm 2 、3346.7 mF / cm 2 , 1432.2 mF / cm 2 ,like Figure 4 shown.
[0063] The test results show that the aerogel electrodes formed by the compounding of cellulose and carbon conductive materials and then polymerization of pyrrole for 2, 4, 6 and 8 hours, due to the doping of polypyrrole, all four samples as supercapacitor electrodes showed reversible Faraday pseudocapacitive behavior of redox reaction during the charge and discharge process, indicating that the membrane material obtained by compounding the dissolving pulp with carbon conductive materials and then polymerizing pyrrole has excellent performance as a supercapacitor electrode.
[0064] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material from a lithium bromide solution, characterized in that: The following steps are involved: S1, adding the dissolving pulp into a lithium bromide aqueous solution to carry out a dissolution reaction to obtain a cellulose solution; S2, adding the carbon conductive material into the cellulose solution for dispersion to obtain a dissolving pulp / carbon conductive material film; S3, soaking the dissolving slurry / carbon conductive material film in a mixed solution containing pyrrole monomer and dopant, and then adding it into an oxidant solution to carry out polymerization reaction, so as to obtain a dissolving slurry / carbon conductive material / polypyrrole composite film material.
2. The method for preparing dissolving pulp / carbon conductive material / polypyrrole composite film material from lithium bromide solution according to claim 1, characterized in that: In step S1, the molar ratio of lithium bromide to water in the lithium bromide aqueous solution is 1:3-3.
5.
3. The method for preparing dissolving pulp / carbon conductive material / polypyrrole composite film material from lithium bromide solution according to claim 1, characterized in that: In step S1, the degree of polymerization of the dissolving pulp is 500-900, and the α-cellulose content is greater than 91%; the mass fraction of the dissolving pulp is 0.3-1.0%, the temperature of the dissolution reaction is 120-130°C, the dissolution time is 15-30 min, and the stirring rate is 800-1200 rmp.
4. The method for preparing dissolving pulp / carbon conductive material / polypyrrole composite film material from lithium bromide solution according to claim 1, characterized in that: In step S2, the carbon conductive material is a compound of carbon nanotubes and reduced graphene oxide, and the mass ratio of the carbon nanotubes, reduced graphene oxide and dissolving pulp is 1:1:1; Preferably, the dispersion time is 30 to 60 min, and the membrane material obtained after the dispersion is washed to neutrality and dried to obtain a dissolving slurry / carbon conductive material membrane.
5. The method for preparing dissolving pulp / carbon conductive material / polypyrrole composite film material from lithium bromide solution according to claim 1, characterized in that: In step S3, the concentration of the pyrrole monomer is 0.5-1.0 mol / L; the molar ratio of the pyrrole monomer to the dopant in the mixed solution is 1:0.5-3; the dopant is selected from one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sodium p-toluenesulfonate, benzenesulfonic acid, and naphthalenesulfonic acid.
6. The method for preparing dissolving pulp / carbon conductive material / polypyrrole composite film material from lithium bromide solution according to claim 1, characterized in that: In step S3, the oxidant is selected from one or more of ferric chloride, vanadium pentoxide, peracetic acid, ammonium persulfate, hydrogen peroxide, and hydrogen peroxide, the concentration of the oxidant solution is 0.75-1.0 mol / L, and the molar ratio of the oxidant to the pyrrole monomer is 1-2:1; Preferably, the polymerization reaction time is 2 to 8 h.
7. A dissolving pulp / carbon conductive material / polypyrrole composite film material, prepared by the method for preparing a dissolving pulp / carbon conductive material / polypyrrole composite film material using a lithium bromide solution as described in the first aspect.
8. A membrane electrode, characterized in that: It comprises the dissolving pulp / carbon conductive material / polypyrrole composite film material as described in claim 7.
9. A supercapacitor, characterized in that: Comprising the membrane electrode as claimed in claim 8.
10. Use of the dissolving pulp / carbon conductive material / polypyrrole composite film material according to claim 7 in capacitor energy storage devices and supercapacitor electrode materials.