CN110838415B - Aramid nanofiber/carbon nanotube/polyaniline composite film and preparation method thereof - Google Patents
Aramid nanofiber/carbon nanotube/polyaniline composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an aramid nanofiber/carbon nanotube/conductive polyaniline composite film material and a preparation method thereof. The aramid fiber nanofiber/carbon nanotube/conductive polyaniline composite film material is prepared by using aramid fiber nanofibers with high mechanical strength and high flexibility as substrate materials, using a loaded carbon nanotube layer as a current collector, compounding the aramid fiber nanofibers and the conductive polyaniline, and gradually assembling a perfect carbon nanotube conductive layer and a polyaniline pseudocapacitance active layer on the basis of an aramid fiber nanofiber film in a step compounding mode. The thin film electrode material of the invention is 1mA/cm2The area specific capacitance can reach 221mF/cm under the charge-discharge current density2The area specific capacitance can still reach 173mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention rate is 78%, and the material has high mechanical strength, high specific capacity and high rate performance and can be used as a self-supporting flexible electrode material.
Description
Technical Field
The invention belongs to the technical field of polymer composite material preparation, and relates to an aramid nanofiber/carbon nanotube/conductive polyaniline composite film material and a preparation method thereof.
Background
The super capacitor is a novel energy storage device between a battery and a traditional capacitor, and has wide application in the fields of new energy power generation systems, distributed energy storage systems, new energy automobiles, aerospace equipment and the like. With the development of commercialization of portable electronic devices and hybrid electric vehicles, practical requirements for flexibility and simplification have been placed on electrode materials for supercapacitors. In recent years, due to the advantages of good processability and mechanical properties, novel carbon-based nano materials have been widely applied to flexible electrode materials. Graphene (carbon nanotubes) is used as a current collector with flexible supporting capacity, pseudocapacitance components are compounded with the current collector, the synergistic effect among the components can be well exerted, and an electrode material with both mechanical property and electrochemical property is obtained, so that the preparation of the high-performance flexible supercapacitor (ACS nano,2009, 3, 1745) 1752) is realized. However, the inherent brittleness of the graphene (carbon nanotube) material cannot adapt to the deformation states of bending, folding, twisting and the like which may occur in practical application. For example, the Carbon nanotube film reported in the literature (Carbon,2005,43, 1891-. Patent (CN 103400703a) reports that a carbon nanotube film is used as a carrier, and pseudo-capacitance components are further deposited to assemble a self-supporting electrode material, and this method improves the specific capacitance of the composite material, but also faces the problem of low mechanical properties, and cannot realize the compatibility of the mechanical properties and the electrochemical properties of the electrode. Therefore, the research of the self-supporting flexible electrode material with high mechanical strength and high electrochemical performance, especially high rate performance, becomes a hot research in the current new energy field.
Poly (p-phenylene terephthalamide) (PPTA) is a high-performance para-aramid fiber, and the basic repeating unit is- [ -CO-C6H4-CONH-C6H4NH- ] -. The aramid fiber yarn has the advantages of high strength, high modulus, high temperature resistance, chemical corrosion resistance, strong flame retardance, fatigue resistance, strong stability and the like. The para-aramid fiber is dissolved in dimethyl sulfoxide to obtain the aramid nanofiber (ACS nano,2011,5(9): 6945-. The film material assembled by the aramid nano-fiber has excellent mechanical strength and can be used as an excellent carrier of a self-supporting flexible electrode. For example, aramid nanofibers are compounded with conductive polythiophene to form a flexible electrode material (J.Mater.chem.A., 2016,4: 17324-. However, the electrode material is prepared by means of liquid phase blending, and poor interfacial compatibility among components results in low mechanical strength (76.4MPa) and low mass specific capacitance (111.5F/g).
Polyaniline (PANI), one of the most commonly used conductive polymers, has wide applications in the field of supercapacitor electrode materials. The patent (CN105111507A) reports that polyaniline is polymerized on the surface of bacterial cellulose and then is blended with carbon nano to assemble a self-supporting flexible electrode. However, this method has the following problems: (1) the electrochemical multiplying power performance of the electrode material is weakened due to poor conductivity of polyaniline, although the multiplying power performance of the material can be improved by increasing the loading capacity of the carbon nano tubes, the specific capacitance of the material is inevitably reduced greatly; (2) the electrode material has larger thickness, so that the flexibility of the material is limited, and the component falling condition caused by internal stress relaxation can be caused by large deformation; (3) the effective interfacial force between the carbon nano tube and the cellulose is lacked, and the high mechanical strength cannot be endowed to the electrode material.
Disclosure of Invention
The invention aims to provide an aramid nanofiber/carbon nanotube/conductive polyaniline composite film material with high mechanical strength and high rate performance and a preparation method thereof. The invention takes aramid nano-fiber with high mechanical strength and high flexibility as a substrate material, takes a loaded carbon nanotube layer as a current collector, and is compounded with conductive polyaniline to prepare the electrode material with high mechanical strength, high specific capacitance and high rate performance, and the electrode material can be used as a flexible self-supporting electrode material.
The technical solution for realizing the purpose of the invention is as follows:
the preparation method of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material comprises the following specific steps:
(1) dissolving PPTA spinning fibers by adopting a dimethyl sulfoxide (DMSO)/KOH system to prepare an aramid fiber nano fiber solution;
(2) dispersing the carbon nano tube in a surfactant by adopting a stirring auxiliary ultrasonic method to prepare a carbon nano tube dispersion liquid, wherein the surfactant is selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or sodium diisooctyl succinate sulfonate;
(3) adding water into the aramid nano-fiber solution, stirring at room temperature, and aging and defoaming the obtained mixed gel system;
(4) assembling the mixed system obtained in the step (3) into an aramid nanofiber gel film by adopting a vacuum filtration method;
(5) adding a carbon nano tube dispersion liquid, assembling a carbon nano tube film on the aramid nano fiber gel film obtained in the step (4) by adopting a vacuum filtration method to obtain an aramid nano fiber/carbon nano tube composite film;
(6) washing the aramid nanofiber/carbon nanotube composite film to remove redundant surfactant, and then drying, wherein the loading capacity of the carbon nanotube is 0.25-2 mg/cm2；
(7) Soaking a dry aramid fiber nanofiber/carbon nanotube composite film serving as a working electrode in a sulfuric acid solution of aniline to perform anodic oxidation polymerization, maintaining the constant potential at 0.8V for 0.5-1 min to perform a polyaniline nucleation reaction, and then performing a constant current density at 0.25-1.98 mA/cm2And maintaining for 1-10 min for polymerization reaction, and washing and drying to obtain the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material.
Further, in the step (1), the concentration of the aramid nanofiber solution is 2-10 mg/mL, the dissolving time is two weeks, the dissolving temperature is room temperature, and the average size of the aramid nanofiber is as follows: the diameter is 30-40 nm and the length is 5-10 μm.
Further, in the step (2), the preparation process of the carbon nanotube dispersion liquid comprises: adding carbon nano tubes into an aqueous solution of a surfactant, stirring until the mixture is uniformly mixed, performing ultrasonic dispersion, wherein the ultrasonic power is 280W, the ultrasonic time is 2-4 h, the ultrasonic temperature is kept below 20 ℃, and after the ultrasonic treatment is finished, placing the dispersion in an ice water bath and aging for 2-6 h to defoam; the concentration of the surfactant is 2-10 mg/mL, and the concentration of the carbon nano tube is 1-5 mg/mL.
Further, in the step (3), 125-200 mL of water is added into every 100mL of aramid nano-fiber solution; stirring for 2-4 h at room temperature; the aging time at room temperature is more than 2 h.
Further, in the steps (4) and (5), a sand core funnel is adopted by the suction filtration device to prepare a microporous filter membrane with the diameter of 47mm, and the vacuum suction filtration pressure is-0.1 MPa.
Further, in the step (6), the washing method comprises the steps of dripping water on the surface of the aramid nano-fiber/carbon nano-tube composite film, and then carrying out vacuum filtration to remove redundant surfactant; the drying procedure is drying at room temperature for 24-48 h, and then vacuum drying at 50-60 ℃ for 20-24 h.
Further, in the step (7), the size of the aramid nano-fiber/carbon nanotube composite film electrode is 1 × 1cm2(ii) a The concentration of the sulfuric acid solution is 1M, and the concentration of the aniline is 0.3M; the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl.
Compared with the prior art, the invention has the following remarkable advantages:
(1) the self-supporting flexible electrode material with high mechanical strength and high multiplying power is prepared by taking the aramid nano-fiber film as a mechanical support, taking the carbon nano-tube film as a current collector and taking the conductive polyaniline as an electrochemical active functional component.
(2) The carbon nano tube conducting layer and the polyaniline active layer are assembled step by step in a cascade compounding mode, the structure of the aramid nano fiber/carbon nano tube/polyaniline film is controlled by adjusting the using amount of the carbon nano tube and the polyaniline, and the flexible electrode material with mechanical property and multiplying power performance is prepared. For example, when the current density for aniline polymerization is 0.25mA/cm2Then, the obtained thin film electrode material is at 1mA/cm2The area specific capacitance can reach 221mF/cm under the charge-discharge current density2The area specific capacitance can still reach 173mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 78%.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an aramid nanofiber/carbon nanotube/conductive polyaniline composite film material;
FIG. 2 is a stress-strain curve diagram of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material;
FIG. 3 is a cyclic voltammetry curve (scan rate is 100mV/s) of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material in a sulfuric acid electrolyte;
FIG. 4 is a cyclic voltammetry curve (scan rate is 10-200 mV/s) of an aramid nanofiber/carbon nanotube/conductive polyaniline composite film material in a sulfuric acid electrolyte;
fig. 5 is a rate performance diagram of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material.
Detailed Description
The invention is further illustrated by the following specific examples and the accompanying drawings.
The schematic diagram of the preparation process of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material is shown in fig. 1. The PPTA used in the following examples is commercially available kevlar spun fiber.
Example 1
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 2mg/mL aramid nanofiber solution.
Weighing carbon nano tubes, adding sodium dodecyl benzene sulfonate solution (the concentration of the solution is 5mg/mL), and stirring until the mixture is uniformly mixed. And (3) transferring the reaction system into water bath ultrasonic waves, performing ultrasonic dispersion for more than 2 hours at the power of 280W, assisting an ice water bath in the ultrasonic process, and controlling the temperature to be not more than 20 ℃. And then placing the mixed system in an ice water bath for aging for more than 2 hours to obtain 3mg/mL carbon nanotube dispersion liquid.
Adding 50mL of deionized water into 25mL of aramid nano-fiber solution, and violently stirring for more than 2h at room temperature to obtain a gel system of the aramid nano-fiber. The system is aged for 2 hours at room temperature, bubbles are removed, and the aramid nano-fiber gel film is prepared by vacuum filtration treatment.
Slowly dripping the carbon nano tube dispersion liquid into a filter cup, completely covering the gel film, and carrying out vacuum filtration treatment to obtain the aramid nano fiber/carbon nano tube gel film. Drying the composite membrane at room temperature for more than 24h, and then vacuum drying at 60 ℃ for 24h to obtain the carbon nano tube with the loading of 1mg/cm2Aramid nano-fiberA carbon nanotube composite film.
1.27mL of aniline monomer is dissolved in 45mL of 1M sulfuric acid solution, and the mixture is stirred for more than 1 hour until the mixture is uniformly mixed, so that the polymer electrolyte with the aniline concentration of 0.3M is obtained. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid fiber nanofiber/carbon nanotube composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is prepolymerized for 1min under the anode voltage of 0.8V to nucleate polyaniline on the carbon nano-tube, and then switched to 0.25mA/cm2The constant current polymerization is carried out, and the reaction is carried out for 10min to obtain the aramid nano-fiber/carbon nano-tube/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode is 226MPa and is 1mA/cm2The area specific capacitance can reach 221mF/cm under the charge-discharge current density2The area specific capacitance can still reach 173mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 78%.
Example 2
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain an aramid nanofiber solution. Obtaining the aramid nano-fiber solution of 5 mg/mL.
Weighing carbon nano tubes, adding a sodium dodecyl sulfate solution (the concentration of the solution is 4mg/mL), and stirring until the mixture is uniformly mixed. And (3) transferring the reaction system into water bath ultrasonic waves, performing ultrasonic dispersion for more than 2 hours at the power of 280W, assisting an ice water bath in the ultrasonic process, and controlling the temperature to be not more than 20 ℃. And then placing the mixed system in an ice water bath for aging for more than 2 hours to obtain 2mg/mL carbon nanotube dispersion liquid.
Weighing 25mL of aramid nano-fiber solution, placing the solution in a reactor, adding 50mL of deionized water, and violently stirring at room temperature for more than 2 hours to obtain an aramid nano-fiber gel system. The system is aged for 2 hours at room temperature, bubbles are removed, and the aramid nano-fiber gel film is prepared by vacuum filtration treatment.
Slowly dripping the carbon nano tube suspension into a filter cup, completely covering the gel film, and carrying out vacuum filtration treatment to obtain the aramid nano fiber/carbon nano tube gel film. Drying the composite membrane at room temperature for more than 24h,then vacuum drying for 24h at 60 ℃ to obtain the carbon nano tube with the loading of 0.5mg/cm2The aramid nano-fiber/carbon nano-tube composite film.
1.27mL of aniline monomer is dissolved in 45mL of 1M sulfuric acid solution, and the mixture is stirred for more than 1 hour until the mixture is uniformly mixed, so that the polymer electrolyte with the aniline concentration of 0.3M is obtained. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid fiber nanofiber/carbon nanotube composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is prepolymerized for 1min under the anode voltage of 0.8V to nucleate polyaniline on the carbon nano-tube, and then switched to 0.5mA/cm2The constant current polymerization is carried out, and the reaction is carried out for 10min to obtain the aramid nano-fiber/carbon nano-tube/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode is 249MPa and is 1mA/cm2The area specific capacitance can reach 179mF/cm under the charge-discharge current density2The area specific capacitance can still reach 160mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 89%.
Example 3
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 10mg/mL aramid nanofiber solution.
Weighing carbon nano tubes, adding a diisooctyl succinate sodium sulfonate solution (the concentration of the solution is 2mg/mL), and stirring until the mixture is uniformly mixed. And (3) transferring the reaction system into water bath ultrasonic waves, performing ultrasonic dispersion for more than 2 hours at the power of 280W, assisting an ice water bath in the ultrasonic process, and controlling the temperature to be not more than 20 ℃. And then placing the mixed system in an ice water bath for aging for more than 2 hours to obtain 1mg/mL carbon nanotube dispersion liquid.
Weighing 25mL of aramid nano-fiber solution, placing the solution in a reactor, adding 50mL of deionized water, and violently stirring at room temperature for more than 2 hours to obtain an aramid nano-fiber gel system. The system is aged for 2 hours at room temperature, bubbles are removed, and the aramid nano-fiber gel film is prepared by vacuum filtration treatment.
Slowly dripping the carbon nano tube water suspension into a filter cup, completely covering the gel film, and performing vacuum filtration to obtain the aramid nano fiberA carbon nanotube gel film. Drying the composite membrane at room temperature for more than 24h, and then vacuum drying at 60 ℃ for 24h to obtain the carbon nano tube with the loading of 0.25mg/cm2The aramid nano-fiber/carbon nano-tube composite film.
1.27mL of aniline monomer is dissolved in 45mL of 1M sulfuric acid solution, and the mixture is stirred for more than 1 hour until the mixture is uniformly mixed, so that the polymer electrolyte with the aniline concentration of 0.3M is obtained. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid fiber nanofiber/carbon nanotube composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is prepolymerized for 1min under the anode voltage of 1V to nucleate polyaniline on the carbon nano tube, and then is switched to 1mA/cm2The constant current polymerization is carried out, and the reaction is carried out for 5min to obtain the aramid nano-fiber/carbon nano-tube/conductive polyaniline composite film electrode. The tensile strength of the composite film electrode is 275MPa and is 1mA/cm2The area specific capacitance can reach 172mF/cm under the charge-discharge current density2The area specific capacitance can still reach 157mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 91%.
Example 4
Weighing 1g of Kevlar yarn and 1.5g of KOH, adding DMSO, and stirring at 25 ℃ for 14 days to obtain a 5mg/mL aramid nanofiber solution.
Weighing carbon nano tubes, adding sodium dodecyl benzene sulfonate solution (the concentration of the solution is 7mg/mL), and stirring until the mixture is uniformly mixed. And (3) transferring the reaction system into water bath ultrasonic waves, performing ultrasonic dispersion for more than 2 hours at the power of 280W, assisting an ice water bath in the ultrasonic process, and controlling the temperature to be not more than 20 ℃. And then placing the mixed system in an ice water bath for aging for more than 2 hours to obtain 5mg/mL carbon nanotube dispersion liquid.
Weighing 25mL of aramid nano-fiber solution, placing the solution in a reactor, adding 50mL of deionized water, and violently stirring at room temperature for more than 2 hours to obtain an aramid nano-fiber gel system. The system is aged for 2 hours at room temperature, bubbles are removed, and the aramid nano-fiber gel film is prepared by vacuum filtration treatment.
Slowly dripping the carbon nano tube suspension into a filter cup to completely cover the filter cupAnd (3) carrying out vacuum filtration treatment on the gel film to obtain the aramid nano-fiber/carbon nano-tube gel film. Drying the composite membrane at room temperature for more than 24h, and then vacuum drying at 60 ℃ for 24h to obtain the carbon nano tube with the loading of 1.8mg/cm2The aramid nano-fiber/carbon nano-tube composite film.
1.27mL of aniline monomer is dissolved in 45mL of 1M sulfuric acid solution, and the mixture is stirred for more than 1 hour until the mixture is uniformly mixed, so that the polymer electrolyte with the aniline concentration of 0.3M is obtained. The electrochemical deposition of polyaniline adopts a three-electrode system to cut the aramid fiber nanofiber/carbon nanotube composite film into 1 multiplied by 1cm2The bulk thin film of (1) is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. The system is prepolymerized for 1min under the anode voltage of 1.0V to nucleate polyaniline on the carbon nano-tube, and then switched to 1.98mA/cm2The constant current polymerization is carried out for 1min, and the aramid fiber/carbon nano tube/conductive polyaniline composite film electrode is obtained. The tensile strength of the composite film electrode is 175MPa and is 1mA/cm2The area specific capacitance can reach 170mF/cm under the charge-discharge current density2The area specific capacitance can still reach 150mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 88%.
Comparative example 1
The method of example 1 was repeated with the specified amounts of the components, but without the conductive polyaniline in the material composition. The tensile strength of the film was 234MPa, 1mA/cm2The area specific capacitance is 37mF/cm under the charge-discharge current density2The area specific capacitance is 26mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 70%.
Comparative example 2
The method of example 1 was repeated with the specified amounts of the components, but without the carbon nanotubes and the conductive polyaniline in the material composition. The tensile strength of the film is 255MPa, and the film has no electrochemical behavior.
Comparative example 3
The method of example 1 is repeated according to the specified content of each component, but the aramid nanofiber/carbon nanotube film is prepared by blending the same amount of the aramid nanofiber dispersion and the carbon nanotube dispersion in example 1 and then performing vacuum filtration treatment. The tensile strength of the film is 215MPa, and the polyaniline cannot be continuously deposited without conductivity.
Comparative example 4
The method of example 1 was repeated with the specified contents of the respective components, but the constant current deposition time of polyaniline was changed to 20 min. The tensile strength of the film is 165MPa, and the composite film electrode is at 1mA/cm2Under the charge-discharge current density, the area specific capacitance can reach 158mF/cm2And the area specific capacitance is 95mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 60%. Too long deposition time may cause the mechanical properties of the composite film to be reduced.
Comparative example 5
The method of example 1 was repeated with the specified contents of the respective components, but the deposition pattern of polyaniline was changed to potentiostatic polymerization at 0.8V anode voltage for 10 minutes. The tensile strength of the film is 223MPa, and the composite film electrode is at 1mA/cm2The area specific capacitance can reach 120mF/cm under the charge-discharge current density2The area specific capacitance is 60mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 50%.
Comparative example 6
The process of example 1 was repeated with the specified amounts of the components, but the aramid nanofibers were replaced with polyethylene terephthalate (PET). The obtained PET/carbon nanotube composite film was used as a working electrode, and was prepolymerized at an anode voltage of 0.8V, and according to the electrochemical polymerization procedure of example 1, a PET/carbon nanotube/polyaniline composite film could not be prepared, and the carbon nanotubes were peeled off from the PET surface under the action of water.
Comparative example 7
The procedure of example 1 was repeated with the specified contents of the respective components, except that the concentration of the aqueous dispersion of carbon nanotubes was 10mg/mL and the loading of carbon nanotubes was 4mg/cm2. Excessive carbon nanotube loading causes the carbon nanotube layer to fall off from the aramid fiber film, and polyaniline deposition cannot be performed.
Comparative example 8
Repeatedly implemented according to the content of each componentThe method of example 1, but the surfactant was dodecylaminopropionic acid (solution concentration 15 mg/mL). The tensile strength of the film was 210MPa at 1mA/cm2The area specific capacitance is 203mF/cm under the charge-discharge current density2And the area specific capacitance is 140mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 69%.
Comparative example 9
The method of example 1 was repeated with the specified amounts of the components, but the carbon nanotubes were replaced by graphene in the material composition. The tensile strength of the film was 243MPa at 1mA/cm2Under the charge-discharge current density, the area specific capacitance is 198 mF/cm2And the area specific capacitance is 56mF/cm under the charge-discharge current density of 30 multiplying power2The capacity retention was 28%.
Table 1 shows the data of the performance tests of examples 1 to 4 and comparative examples 1 to 9.
TABLE 1
The carbon nanotube conducting layer and the polyaniline pseudocapacitance active layer which are completely assembled step by step on the basis of the aramid fiber nanofiber film by adopting a step compounding mode, the self-supporting flexible electrode material with high mechanical strength and high multiplying power is prepared, the multiplying power performance of the electrode material is greatly improved, and the compatibility degree of the mechanical property and the electrochemical property of the flexible electrode material is obviously improved.
Claims (9)
1. The preparation method of the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material is characterized by comprising the following specific steps of:
(1) dissolving PPTA spinning fibers by adopting a DMSO/KOH system to prepare an aramid nano fiber solution;
(2) dispersing the carbon nano tube in a surfactant by adopting a stirring auxiliary ultrasonic method to prepare a carbon nano tube dispersion liquid, wherein the surfactant is selected from sodium dodecyl benzene sulfonate, sodium dodecyl sulfate or sodium diisooctyl succinate sulfonate;
(3) adding water into the aramid nano-fiber solution, stirring at room temperature, aging and defoaming the obtained mixed gel system, adding 125-200 mL of water into every 100mL of aramid nano-fiber solution, stirring at room temperature for 2-4 h, and aging at room temperature for more than 2 h;
(4) assembling the mixed system obtained in the step (3) into an aramid nanofiber gel film by adopting a vacuum filtration method;
(5) adding a carbon nano tube dispersion liquid, assembling a carbon nano tube film on the aramid nano fiber gel film obtained in the step (4) by adopting a vacuum filtration method to obtain an aramid nano fiber/carbon nano tube composite film;
(6) washing the aramid nanofiber/carbon nanotube composite film to remove redundant surfactant, and then drying, wherein the loading capacity of the carbon nanotube is 0.25-2 mg/cm2；
(7) Soaking a dry aramid fiber nanofiber/carbon nanotube composite film serving as a working electrode in a sulfuric acid solution of aniline to perform anodic oxidation polymerization, maintaining the constant potential at 0.8V for 0.5-1 min to perform a polyaniline nucleation reaction, and then performing a constant current density at 0.25-1.98 mA/cm2And maintaining for 1-10 min for polymerization reaction, and washing and drying to obtain the aramid nanofiber/carbon nanotube/conductive polyaniline composite film material.
2. The preparation method of claim 1, wherein in the step (1), the concentration of the aramid nanofiber solution is 2-10 mg/mL, the dissolving time is two weeks, the dissolving temperature is room temperature, and the average size of the aramid nanofibers is as follows: the diameter is 30-40 nm, and the length is 5-10 mm.
3. The method according to claim 1, wherein in the step (2), the carbon nanotube dispersion is prepared by a process comprising: adding the carbon nano tube into an aqueous solution of a surfactant, stirring until the mixture is uniformly mixed, performing ultrasonic dispersion, wherein the ultrasonic power is 280W, the ultrasonic time is 2-4 h, the ultrasonic temperature is kept below 20 ℃, and after the ultrasonic treatment is finished, placing the dispersion in an ice water bath for aging for 2-6 h to defoam.
4. The method according to claim 1, wherein in the step (2), the concentration of the surfactant is 2-10 mg/mL, and the concentration of the carbon nanotube is 1-5 mg/mL.
5. The preparation method according to claim 1, wherein in the steps (4) and (5), the suction filtration device adopts a sand core funnel to prepare the microfiltration membrane with the diameter of 47mm, and the vacuum filtration pressure is-0.1 MPa.
6. The preparation method according to claim 1, wherein in the step (6), water is dripped on the surface of the aramid nano-fiber/carbon nanotube composite film, and then vacuum filtration is carried out to remove the excessive surfactant.
7. The preparation method according to claim 1, wherein in the step (6), the drying process is carried out at room temperature for 24-48 h, and then vacuum drying is carried out at 50-60 ℃ for 20-24 h.
8. The preparation method of claim 1, wherein in the step (7), the size of the aramid nanofiber/carbon nanotube composite film electrode is 1 x 1cm2(ii) a The concentration of the sulfuric acid solution is 1M, and the concentration of the aniline is 0.3M; the counter electrode is a platinum sheet, and the reference electrode is Ag/AgCl.
9. The aramid nanofiber/carbon nanotube/conductive polyaniline composite film material prepared by the preparation method according to any one of claims 1 to 8.
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