CN110931261B - Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance - Google Patents
Preparation method of flexible fabric supercapacitor electrode material with graphene/polypyrrole as active substance Download PDFInfo
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Abstract
The invention belongs to the technical field of super capacitors, and particularly relates to a preparation method of a flexible fabric super capacitor electrode material with graphene/polypyrrole as an active substance. Firstly, swelling and crosslinking the carboxymethyl chitosan/viscose blended non-woven fabric, then preparing a graphene/non-woven fabric conductive material by adopting a dipping-drying method, and then polymerizing a pyrrole monomer onto the graphene/non-woven fabric conductive material by adopting an in-situ chemical oxidation polymerization method to obtain the flexible fabric supercapacitor electrode material taking the graphene/polypyrrole as an active substance. The flexible substrate material adopted by the invention is carboxymethyl chitosan/viscose blended non-woven fabric, wherein carboxymethyl chitosan is a water-soluble high polymer material, the swelling of carboxymethyl chitosan in a cross-linking agent aqueous solution promotes the specific surface area of the fabric to be increased, and the carboxymethyl chitosan can be filled in pores in the fabric, so that the space utilization rate of the fabric can be greatly improved, and the carboxymethyl chitosan/viscose blended non-woven fabric is beneficial to loading a large amount of electroactive substances and is an ideal support material for a flexible electrode.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a preparation method of a flexible fabric super capacitor electrode material with graphene/polypyrrole as an active substance.
Background
With the rapid development of global economy and industrial technology, energy problems become a focus of attention in all countries of the world, and the development of renewable energy conversion and storage devices is particularly critical. Development of high-performance energy devices to meet future requirements for high energy density, high power density and long cycle life has been a focus of research. The super capacitor is a novel electrochemical energy storage device between a traditional capacitor and a battery, has the advantages of high charging and discharging speed, long cycle life, environmental friendliness and the like, and is considered to be an important choice for future power supplies.
With the increasing demand for wearable electronic devices, the comfort of the wearable electronic devices is also receiving more and more attention of researchers, and adding active materials on a flexible substrate by chemical deposition, electrodeposition, coating and the like is a common preparation method of flexible electrodes, and the researchers assemble the prepared flexible electrodes and a flexible electrolyte together to prepare a solid-state flexible supercapacitor. Researchers at home and abroad mainly use different active materials (mainly carbon materials, metal oxides and conductive high polymer materials) to prepare flexible supercapacitors with different forms on a plurality of flexible base materials (mainly metal, plastic, paper, fabric and the like). However, the one-dimensional supercapacitors with plastic, paper or metal substrates are still lack of wearing comfort due to the fact that the electrode substrate materials of the supercapacitors are different from the clothing fabrics in daily life. Based on the above disadvantages, research into flexible supercapacitors having textile fibers as electrode substrates in daily life has begun to emerge. In addition, the fabric has the characteristics of softness, good air permeability, stretchability and the like, and is considered as an ideal substrate material for designing and preparing wearable energy storage devices.
The conductive polymer is a polymer material with conductivity, has a unique structure and excellent physical and chemical properties, is easy to synthesize, has high electrochemical activity, good conductivity and low cost, is suitable for being used as an electrode of a super capacitor, and becomes a new hot spot for research of super capacitors in recent years. The polypyrrole has the characteristics of light weight, low cost and no toxicity, and the flexible and wearable characteristic of the fabric electrode is better met. The molecular chain of the polypyrrole is easy to expand or contract in the charging and discharging processes to be damaged, so that the cycle performance of the supercapacitor becomes poor when the polypyrrole is used as an electrode material, and the capacitance performance is obviously attenuated.
Disclosure of Invention
The invention provides a preparation method of a flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active substance. Aims to prepare a fabric electrode with large mass load and high area specific capacitance.
The technical scheme of the invention is realized as follows:
the preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active substance comprises the following steps:
(1) soaking the carboxymethyl chitosan/viscose blended non-woven fabric into a cross-linking agent aqueous solution for 3-15 minutes, taking out, placing in an oven for cross-linking and drying to obtain a cross-linked carboxymethyl chitosan/viscose blended non-woven fabric;
(2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric obtained in the step (1) in graphene water dispersion for 2-30 minutes, taking out the non-woven fabric, drying the non-woven fabric in a drying oven, and drying to obtain a graphene/non-woven fabric composite material;
(3) and (3) soaking the graphene/non-woven fabric composite material obtained in the step (2) in a pyrrole aqueous solution for 0.5-2 hours, dropwise adding an iron trioxide aqueous solution into the reaction solution, continuing to react for 0.5-4 hours after dropwise adding, finishing the reaction, washing the material with water after the reaction is finished, and drying to obtain the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active substance.
The mass percentage of the carboxymethyl chitosan fiber in the carboxymethyl chitosan/viscose blended non-woven fabric in the step (1) is 20-60%.
The mass percentage of the cross-linking agent in the cross-linking agent aqueous solution in the step (1) is 0.05-1%, the pH value is 4-5, and the cross-linking agent is any one of glutaraldehyde, adipaldehyde and succinaldehyde.
The temperature of the crosslinking drying in the step (1) is 40-80 ℃, and the time is 0.5-2 hours.
The concentration of the graphene aqueous dispersion in the step (2) is 1-2mg/mL, the drying temperature is 50-80 ℃, and the drying time is 1-3 hours.
In the step (3), the concentration of the pyrrole aqueous solution is 0.1-1.0mol/L, and the concentration of the ferric trioxide aqueous solution is 0.1-1.0 mol/L; the mass ratio of the pyrrole aqueous solution to the ferric trioxide aqueous solution is 1: (1-2).
The dropping time of the aqueous solution of ferric trioxide in the step (3) is 0.5 hour.
The temperature of the reaction system is maintained at 0-15 ℃ in the whole process of the step (3).
The invention has the following beneficial effects:
(1) the flexible substrate material adopted by the invention is carboxymethyl chitosan/viscose blended non-woven fabric (purchased from Guangzhou Meitianyuan non-woven products, Inc., with the surface density of 40g/m2) The carboxymethyl chitosan is a water-soluble polymer material, the swelling of the carboxymethyl chitosan in a cross-linking agent aqueous solution promotes the specific surface area of the fabric to be increased, and the carboxymethyl chitosan can fill pores in the fabric, can greatly improve the space utilization rate of the fabric, is beneficial to loading a large amount of electroactive substances, and is an ideal support material for a flexible electrode.
(2) The existence of carboxymethyl chitosan enables the surface of the fabric to be provided with corresponding positive charges, under the action of electrostatic attraction, graphene with negative charges is uniformly loaded on the surface of fibers in the fabric to form a three-dimensional network structure with good conductivity, a high-conductivity flexible substrate is prepared, an active material with high pseudocapacitance is deposited on the surface of the substrate, and the flexible electrode for the flexible supercapacitor with excellent electrochemical performance and mechanical performance is obtained.
(3) The carboxymethyl chitosan has a large amount of active amino and hydroxyl, and can form a hydrogen bond effect with nitrogen atoms on a conductive polymer polypyrrole heterocyclic ring, the interaction between an active material and a fabric substrate can be enhanced through the hydrogen bond effect, the interface impedance is reduced, the utilization rate of the active substance is improved, and the high-active substance load, high surface area and high conductivity flexible fabric electrode is obtained. The method converts the fiber fabric on the market into the flexible wearable solid-state supercapacitor with excellent electrochemical performance through simpler steps, and provides a new strategy for preparing flexible energy storage equipment with excellent performance.
(4) The method for preparing the fabric electrode is simple, low in cost, mild in condition and beneficial to large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a comparative photograph of optical photographs, in which (a) chitosan/viscose blended nonwoven fabric, (b) cross-linked nonwoven fabric, (c) graphene-adsorbed nonwoven fabric, and (d) flexible fabric capacitor electrode.
Fig. 2 is a comparative scanning electron microscope image, in which (a) chitosan/viscose blended nonwoven fabric, (b) cross-linked nonwoven fabric, (c) graphene-adsorbed nonwoven fabric, and (d) flexible fabric capacitor electrode.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 0.9% glutaraldehyde aqueous solution, adjusting the pH value of the glutaraldehyde aqueous solution to 4.5 by using hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 x 4cm) with the carboxymethyl chitosan fiber content of 30% in the glutaraldehyde aqueous solution for 5 minutes, taking out the carboxymethyl chitosan/viscose blended non-woven fabric, and placing the carboxymethyl chitosan/viscose blended non-woven fabric in an oven to be cross-linked and dried for 1.5 hours at the temperature of 45 ℃ to obtain the cross-linked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1mg/ml for 2 minutes, taking out the graphene water dispersion, drying the graphene water dispersion for 3 hours at 50 ℃ in an oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.3mol/L pyrrole aqueous solution for 0.5 hour, dropwise adding 50 g of 0.6mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 3 hours after dropwise adding is finished, finishing the reaction, maintaining the temperature of the reaction system at 12 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 6627mF/cm2。
Example 2
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing a succinaldehyde aqueous solution with the concentration of 0.3 percent, regulating the pH value of the succinaldehyde aqueous solution to 5 by hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with the carboxymethyl chitosan fiber content of 50 percent into the succinaldehyde aqueous solution for 8 minutes, taking out the carboxymethyl chitosan/viscose blended non-woven fabric, and placing the carboxymethyl chitosan/viscose blended non-woven fabric into an oven to be cross-linked and dried for 1.0 hour at the temperature of 60 ℃ to obtain the cross-linked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 2mg/ml, taking out the graphene water dispersion after soaking for 30 minutes, drying the graphene/viscose blended non-woven fabric for 1 hour at 80 ℃ in an oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.45mol/L pyrrole aqueous solution for 1.5 hours, dropwise adding 50 g of 0.9mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 1 hour after dropwise adding is finished, finishing the reaction, maintaining the temperature of the reaction system at 12 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 8832mF/cm2。
Example 3
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 0.45% of already-dialdehyde aqueous solution, adjusting the pH value to 4.5 by using hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with the carboxymethyl chitosan fiber content of 50% in the already-dialdehyde aqueous solution for 5 minutes, taking out, placing in an oven, and performing crosslinking drying at 50 ℃ for 1.2 hours to obtain the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1.5mg/ml, taking out the graphene water dispersion after soaking for 10 minutes, drying the graphene/viscose blended non-woven fabric for 2.5 hours at the temperature of 60 ℃ in a drying oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.75mol/L pyrrole aqueous solution for 1 hour, dropwise adding 50 g of 1mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 3 hours after the dropwise addition is finished, finishing the reaction, maintaining the temperature of the reaction system at 5 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 8724 mF/cm2。
Example 4
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 0.05% glutaraldehyde aqueous solution, adjusting the pH value to 4 by hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with the carboxymethyl chitosan fiber content of 20% in the glutaraldehyde aqueous solution for 3 minutes, taking out, placing in an oven, and performing crosslinking drying at 80 ℃ for 0.5 hour to obtain the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1.6mg/ml, taking out the graphene water dispersion after soaking for 7 minutes, drying the graphene/viscose blended non-woven fabric for 2.5 hours at 55 ℃ in a drying oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.1mol/L pyrrole aqueous solution for 0.5 hour, dropwise adding 50 g of 0.1mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 0.5 hour after dropwise adding, finishing the reaction, keeping the temperature of the reaction system at 0 ℃ in the whole process, washing the material with water after finishing the reaction, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared in the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the area specific capacitance of the flexible electrode is 5624mF/cm2 under the current density of 2 mA/cm 2.
Example 5
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 1% succinaldehyde aqueous solution, adjusting the pH value to 5 by hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with 60% of carboxymethyl chitosan fiber content in the succinaldehyde aqueous solution for 15 minutes, taking out, and placing in an oven for crosslinking and drying at 40 ℃ for 2 hours to obtain the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1.2mg/ml, taking out the graphene water dispersion after soaking for 25 minutes, drying the graphene/viscose blended non-woven fabric in a drying oven at 70 ℃ for 1.5 hours, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 1mol/L pyrrole aqueous solution, dripping 50 g of 1mol/L ferric trioxide aqueous solution into the reaction solution after soaking for 2 hours, keeping the temperature of the reaction system at 0 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the flexible electrode of the carboxymethyl chitosan/viscose blended non-woven fabric, wherein the dripping time is 0.5 hours, and the reaction is finished after the dripping is finished and continuing to react for 4 hours.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 8336mF/cm2。
Example 6
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing a succinaldehyde aqueous solution with the concentration of 0.7 percent, regulating the pH value of the succinaldehyde aqueous solution to 5 by hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with the carboxymethyl chitosan fiber content of 30 percent into the succinaldehyde aqueous solution for 12 minutes, taking out the carboxymethyl chitosan/viscose blended non-woven fabric, and placing the carboxymethyl chitosan/viscose blended non-woven fabric into an oven to be cross-linked and dried for 0.8 hour at 70 ℃ to obtain the cross-linked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1.3mg/ml, taking out the graphene water dispersion after soaking for 9 minutes, drying the graphene/viscose blended non-woven fabric for 2 hours at 72 ℃ in an oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.2mol/L pyrrole aqueous solution for 1.5 hours, dropwise adding 50 g of 0.4mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 4 hours after dropwise adding, finishing the reaction, keeping the temperature of the reaction system at 0 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is adopted to workThe electrode, the platinum sheet as a counter electrode, the calomel electrode as a reference electrode and the electrolyte as 1mol/L hydrochloric acid aqueous solution, and the test result shows that the flexible electrode is at 2 mA/cm2The area specific capacitance at current density was 7420mF/cm2。
Example 7
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 0.5% already dialdehyde aqueous solution, adjusting the pH value to 4.5 with hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 x 4cm) with the carboxymethyl chitosan fiber content of 40% in the already dialdehyde aqueous solution for 10 minutes, taking out, placing in an oven, and crosslinking and drying at 60 ℃ for 1 hour to obtain the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1mg/ml, taking out the graphene water dispersion after soaking for 11 minutes, drying the graphene/viscose blended non-woven fabric for 3 hours at 50 ℃ in an oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.5mol/L pyrrole aqueous solution for 1 hour, dropwise adding 50 g of 1mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 2 hours after the dropwise addition is finished, finishing the reaction, maintaining the temperature of the reaction system at 10 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 8310mF/cm2
Example 8
The preparation method of the flexible fabric supercapacitor electrode material with graphene/polypyrrole as an active substance in the embodiment comprises the following steps:
(1) preparing 0.2% glutaraldehyde aqueous solution, adjusting the pH value to 4 by hydrochloric acid, immersing the carboxymethyl chitosan/viscose blended non-woven fabric (2 multiplied by 4cm) with 50% carboxymethyl chitosan fiber content in the glutaraldehyde aqueous solution for 10 minutes, taking out, placing in an oven, and performing crosslinking drying at 50 ℃ for 1.5 hours to obtain the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric.
(2) And (2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric into graphene water dispersion with the concentration of 1.9mg/ml, taking out the graphene water dispersion after soaking for 5 minutes, drying the graphene/viscose blended non-woven fabric for 2.3 hours at 65 ℃ in a drying oven, and drying to obtain the graphene/non-woven fabric composite material.
(3) Soaking the graphene/non-woven fabric composite material in 50 g of 0.5mol/L pyrrole aqueous solution for 0.5 hour, dropwise adding 50 g of 0.6mol/L ferric trioxide aqueous solution into the reaction solution for 0.5 hour, continuing to react for 3 hours after dropwise adding is finished, finishing the reaction, maintaining the temperature of the reaction system at 15 ℃ in the whole process, washing the material with water after the reaction is finished, and drying to obtain the carboxymethyl chitosan/viscose blended non-woven fabric flexible electrode.
The prepared flexible electrode was tested by an electrochemical workstation under a three-electrode system:
the flexible motor prepared by the embodiment is used as a working electrode, a platinum sheet is used as a counter electrode, a calomel electrode is used as a reference electrode, and an electrolyte is 1mol/L hydrochloric acid aqueous solution, and test results show that the flexible electrode is 2 mA/cm2The area specific capacitance under the current density is 7122 mF/cm2。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active substance is characterized by comprising the following steps:
(1) soaking the carboxymethyl chitosan/viscose blended non-woven fabric into a cross-linking agent aqueous solution for 3-15 minutes, taking out, placing in an oven for cross-linking and drying to obtain a cross-linked carboxymethyl chitosan/viscose blended non-woven fabric;
(2) soaking the crosslinked carboxymethyl chitosan/viscose blended non-woven fabric obtained in the step (1) in graphene water dispersion for 2-30 minutes, taking out the non-woven fabric, drying the non-woven fabric in a drying oven, and drying to obtain a graphene/non-woven fabric composite material;
(3) soaking the graphene/non-woven fabric composite material obtained in the step (2) in a pyrrole aqueous solution for 0.5-2 hours, dropwise adding an iron trioxide aqueous solution into the reaction solution, continuing to react for 0.5-4 hours after dropwise adding, finishing the reaction, washing the material with water after the reaction is finished, and drying to obtain a flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active substance;
the mass percentage of the cross-linking agent in the cross-linking agent aqueous solution in the step (1) is 0.05-1%, and the pH value is 4-5, wherein the cross-linking agent is any one of glutaraldehyde, adipaldehyde and succinaldehyde; the temperature of the crosslinking drying in the step (1) is 40-80 ℃, and the time is 0.5-2 hours.
2. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active material according to claim 1 is characterized in that: the mass percentage of the carboxymethyl chitosan fiber in the carboxymethyl chitosan/viscose blended non-woven fabric in the step (1) is 20-60%.
3. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active material according to claim 1 is characterized in that: the concentration of the graphene aqueous dispersion in the step (2) is 1-2mg/mL, the drying temperature is 50-80 ℃, and the drying time is 1-3 hours.
4. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active material according to claim 1 is characterized in that: in the step (3), the concentration of the pyrrole aqueous solution is 0.1-1.0mol/L, and the concentration of the ferric trioxide aqueous solution is 0.1-1.0 mol/L; the mass ratio of the pyrrole aqueous solution to the ferric trioxide aqueous solution is 1: (1-2).
5. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active material according to claim 4, is characterized in that: the dropping time of the aqueous solution of ferric trioxide in the step (3) is 0.5 hour.
6. The preparation method of the flexible fabric supercapacitor electrode material taking graphene/polypyrrole as an active material according to claim 4, is characterized in that: the temperature of the reaction system is maintained at 0-15 ℃ in the whole process of the step (3).
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