CN109293918B - Polyaniline nano-cluster and preparation method and device thereof - Google Patents
Polyaniline nano-cluster and preparation method and device thereof Download PDFInfo
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- CN109293918B CN109293918B CN201811032873.5A CN201811032873A CN109293918B CN 109293918 B CN109293918 B CN 109293918B CN 201811032873 A CN201811032873 A CN 201811032873A CN 109293918 B CN109293918 B CN 109293918B
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Abstract
The invention relates to a polyaniline nano-cluster and a preparation method and a device thereof, wherein the preparation method comprises the following steps: and soaking the flexible conductive substrate in an aniline solution, spraying an initiator solution on two sides, carrying out polymerization reaction in a high-voltage electric field, continuing reaction in a low-temperature environment, washing, and drying to obtain the flexible conductive substrate. The preparation device is simple, compact and easy to operate, and can realize continuous and large-scale preparation of the polyaniline nanocluster; the prepared material keeps the inherent porous structure and excellent mechanical property of the flexible conductive base material, the material is light and flexible and can be cut at will, the polyaniline grown on the flexible conductive base material is in a highly oriented nano cluster, and the nano structure can be regulated and controlled through the concentration of reactants and the polymerization condition under a high-voltage electric field; the composite material has wide application in the fields of energy storage materials, sensing materials, electromagnetic shielding materials, antistatic materials, conductive composite materials and the like.
Description
Technical Field
The invention belongs to the field of polyaniline nano-materials and preparation thereof and devices, and particularly relates to a polyaniline nano-cluster and a preparation method and a device thereof.
Background
As a conductive polymer, polyaniline has wide application prospect in many fields such as energy storage materials, sensing materials, electromagnetic shielding materials, antistatic materials, conductive composite materials and the like by virtue of the advantages of low cost, simple synthesis, unique doping phenomenon, good environmental stability, high conductivity and the like. The microstructure, morphology and size of polyaniline have great influence on the performance of polyaniline, and the key to realizing the industrialization is how to design a technical device which is simple, efficient, highly controllable and can be industrialized to construct the nano-structure polyaniline.
The polyaniline nano-structure mainly comprises nano-sheets, nano-rods, nano-tubes and nano-fibers. At present, methods for preparing nano-structured polyaniline mainly include a template method, a self-assembly method, an interfacial polymerization method, an in-situ polymerization method, an electrochemical polymerization method and the like. The picrorhiza et al [ CN 107903427A ] adopts a dilute solution chemical oxidation synthesis method, a matrix material is added into a treated aniline acid solution to obtain a first solution, and then an initiator acid solution is added into the first solution to obtain the polyaniline nanofiber array material, but the preparation efficiency is low due to the low monomer concentration. The method for preparing the conductive polyaniline nanotube by taking maltose as a template has the advantages of simple preparation process, environmental protection, reliability and wide raw material source, but the template needs to be post-treated and is easy to damage the shape structure of the polyaniline. The polyaniline nano-fiber with controllable size is obtained by interfacial polymerization of myrica and the like [ CN 101037504A ], and the method is simple and cheap, does not need post-treatment and a template, but needs an organic solvent. Chengming et al [ CN 106941152A ] adopt an electrodeposition method to obtain a cobaltosic oxide nanorod/polyaniline core-shell array electrode, the method takes the cobaltosic oxide nanorod as a template to electrodeposit polyaniline, and a hollow core-shell array is directly connected with a current collector without any conductive additive, so that the energy density of the battery is improved, but the experimental process is more complicated. In the forest wave generation and the like [ CN 108010750A ], the ultrathin-wall multistage porous carbon is prepared by taking asphalt and additives as raw materials, and the ultrathin-wall multistage porous carbon/polyaniline super capacitor electrode material is prepared by taking the asphalt and the additives as base materials through chemical oxidation, so that the preparation cost is low, the synergistic effect of polyaniline and porous carbon is utilized, and the electrochemical performance of the electrode material is good. But the preparation conditions are relatively harsh and complicated. Zhang Qiuguo et al [ CN 104213243B ] introduce magnetic microsphere in the process of synthesizing polyaniline to influence the polymerization reaction of aniline monomer, thus realizing the preparation of polyaniline nano-fiber with high length-diameter ratio. Yuansheng et al [ CN 105585729B ] are matched with the gold nanoparticles on the surface of the polymer/aminated inorganic nano oxide composite film, so that aniline monomers are directionally self-assembled, and condensation polymerization is carried out through chemical reaction under mild conditions, so that the polyaniline array grows in situ on the surface of the polymer film, but the preparation process needs the gold nanoparticles, and the cost is high.
Although these methods successfully produce nanostructured polyaniline, relatively efficient, simple green, controllable, and industrially applicable synthesis is not easily achieved, and most of the synthetic products are disordered polyaniline nanomaterials. Therefore, it is very important to provide and develop a method and a device suitable for continuously and massively preparing polyaniline nano-materials with an array structure. With the development of wearable/portable electronic products, flexible energy storage devices and portable sensing devices have become a hot point of research. The fabrication of high performance flexible electrodes is critical considering that the electrodes have a critical impact on device performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polyaniline nanocluster and a preparation method and a device thereof, and overcomes the defects that the preparation method in the prior art is not easy to realize relatively high-efficiency, green, simple, controllable and industrialized synthesis, and most of synthetic products are disordered polyaniline nanomaterials.
According to the polyaniline nanocluster, polyaniline grown on the flexible conductive base material is in a highly-oriented nanocluster.
The invention relates to a preparation method of a polyaniline nanocluster, which comprises the following steps:
and soaking the flexible conductive substrate in an aniline solution, spraying an initiator solution on two sides, carrying out polymerization reaction in a high-voltage electric field, continuing reaction in a low-temperature environment, washing, and drying to obtain the polyaniline nanocluster.
The preferred mode of the above preparation method is as follows:
the temperature of the whole reaction process of the preparation method of the polyaniline nanocluster is kept between 0 and 10 ℃.
The flexible conductive base material is conveyed through a conveying system to carry out continuous preparation, wherein the conveying speed of the flexible conductive base material is 0.2-2.5 cm/s; the flexible conductive substrate is one of carbon cloth, carbon paper and graphene film.
The soaking time is 10-120 min, and the spraying speed is 0.01-2 ml/s.
The aniline solution is obtained by dissolving aniline in an acid medium, and the concentration of the aniline solution is 0.1-3.0M; the acid medium is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid and perchloric acid, and the concentration is 0.1-3.0M. The initiator solution is obtained by dissolving an initiator in an acid medium, wherein the concentration of the initiator solution is 0.01-4.0M; the acid medium is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid and perchloric acid, and the concentration is 0.1-3.0M; the initiator is one or more oxidants of persulfate, dichromate, transition metal salt, peroxide and potassium permanganate.
The persulfate is ammonium persulfate and the like, the dichromate is potassium dichromate and the like, the transition metal salt is ferric chloride and the like, and the peroxide is hydrogen peroxide and the like.
The parameters of the polymerization reaction carried out in the high-voltage electric field are as follows: the high-voltage electric field is a flat electric field, the distance between the positive flat electrode and the negative flat electrode is 5-20 cm, the flexible conductive base material is located in the center of the flat electrodes, the applied direct-current high voltage is 5-50 kV, and the polymerization reaction time is 30-240 min.
The method specifically comprises the following steps: the high-voltage electric field is a flat electric field, the distance between the positive flat electrode and the negative flat electrode is 5-20 cm, and the flexible conductive substrate is positioned in the center of the flat electrodes; the applied direct current high voltage is 5-50 kV; the residence time of the high-voltage electric field polymerization system is 30-240 min. The continuous reaction in the low-temperature environment comprises the following steps: the temperature is 0-10 ℃, and the reaction time is 180-330 min.
The method specifically comprises the following steps: the temperature of the low-temperature reaction system is 0-10 ℃, and the residence time of the flexible conductive base material in the low-temperature reaction system is 180-330 min.
The invention relates to application of a polyaniline nanocluster, which is applied to the fields of energy storage materials, sensing materials, electromagnetic shielding materials, antistatic materials, conductive composite materials and the like.
The continuous preparation device for the polyaniline nanoclusters is characterized in that an aniline monomer infiltration system 2, an initiator spraying system 3, a high-voltage electric field polymerization system 4, a low-temperature reaction system 5 and a conveying system 1 are sequentially arranged in the preparation device, a flexible conductive base material sequentially passes through the aniline monomer infiltration system 2, the initiator spraying system 3, the high-voltage electric field polymerization system 4 and the low-temperature reaction system 5 under the traction of the conveying system 1, the temperature of the interior of the preparation device is controlled through a circulating water cooling system 6, and the circulating water cooling system 6 is connected with a temperature controller 7.
Advantageous effects
(1) The composite material prepared by the invention keeps the inherent porous structure and excellent mechanical property of the flexible conductive base material, the weight is light, the flexibility can be cut at will, the polyaniline grown on the flexible conductive base material is in a highly oriented nano cluster, the shape and the size of the nano structure can be regulated and controlled by the concentration of reactants and the polymerization condition under a high-voltage electric field, and the disordered polyaniline nano material in the prior art cannot regulate and control the nano structure;
(2) the invention provides a continuous preparation method and a device of a polyaniline nanocluster.A flexible conductive base material is firstly subjected to an acid solution of aniline by a conveying system, then is sprayed with an initiator acid solution on two sides, and then is sent to a high-voltage electric field for polymerization reaction; then continuing the reaction in a low-temperature environment to realize the continuous preparation of the polyaniline nanocluster;
(3) the continuous preparation method of the polyaniline nanocluster is established on the basis of a simple preparation process and cheap raw materials, and is beneficial to promoting large-scale production and commercial application of flexible devices, the raw materials are easy to obtain and low in cost, no emulsifier or organic solvent is required to be added, the whole reaction is carried out in a water phase, the method is environment-friendly and green, the large-scale preparation of the polyaniline nanocluster can be realized, and the continuous and large-scale preparation cannot be realized in the prior art;
(4) the preparation device is simple and easy to operate, can realize the continuous production of the polyaniline nanocluster, and can simply regulate and control the shape and structure of the polyaniline by regulating the concentration of the aniline monomer, the electric field intensity and the reaction time (see the examples 2-4) to prepare the nano-structure polyaniline with different properties; according to different conductive characteristics and structural characteristics of polyaniline, the polyaniline can be used in the fields of energy storage materials, sensing materials, electromagnetic shielding materials, antistatic materials, conductive composite materials and the like.
Drawings
FIG. 1 is a diagram of an apparatus for continuous preparation of polyaniline nanoclusters designed by the present invention; the system comprises a conveying system 1, an aniline monomer soaking system 2, an initiator spraying system 3, a high-voltage electric field polymerization system 4, a low-temperature reaction system 5, a circulating water cooling system 6 and a temperature controller 7;
FIG. 2 is a scanning electron microscope image of field emission of the polyaniline nanoclusters prepared in example 2 of the present invention;
FIG. 3 is a graph showing the gas-sensitive response of the polyaniline nanoclusters prepared in example 2 to formaldehyde gas;
FIG. 4 is a field emission scanning electron micrograph of the polyaniline nanoclusters prepared in example 3;
FIG. 5 is a graph showing the adsorption performance of the polyaniline nanoclusters prepared in example 3 for chromium ions, wherein the inset is a comparison of the potassium dichromate solution before and after adsorption;
FIG. 6 is a scanning electron micrograph of the polyaniline nanoclusters prepared in example 4 by field emission;
fig. 7 is a cyclic voltammetry curve of the polyaniline nanocluster prepared in example 4 under different mechanical states, wherein an inset is a demonstration graph of the different mechanical states.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The apparatus of FIG. 1 was used in all the examples.
Example 1
The device for continuously preparing the polyaniline nanocluster is shown in figure 1: comprises a conveying system 1, an aniline monomer infiltration system 2, an initiator spraying system 3, a high-voltage electric field polymerization system 4, a low-temperature reaction system 5, a circulating water cooling system 6 and a temperature controller 7.
Wherein the flexible conductive substrate is firstly soaked in an aniline monomer soaking system 2 for 10-330 min through a conveying system (the conveying speed is 0.2-2.5 cm/s)1, and then is conveyed to an initiator spraying system 3 for double-sided spraying (the spraying speed is 0.01-2 ml/s); timely transmitting the mixture to a high-voltage electric field polymerization system 4 for reaction, wherein the size of a high-voltage power supply is 5-50 kV, the distance between a positive plate electrode and a negative plate electrode is 5-20 cm, and a flexible conductive substrate is positioned in the center of the plate electrodes; the residence time of the high-voltage electric field polymerization system is 30-240 min, and then the reaction is continued for 180-330 min in the low-temperature reaction system 5; the whole device adjusts the temperature (0-10 ℃) through a water cooling system 6 and a temperature controller 7.
Example 2
Weighing 1.396kg (15mol) of aniline, adding the aniline into 5L of 3M hydrochloric acid aqueous solution to prepare an acid solution of aniline, and injecting the acid solution into an aniline monomer infiltration container; 3.423kg (15mol) of ammonium persulfate was weighed and added to 5L of a 3M aqueous hydrochloric acid solution to prepare an acidic solution of ammonium persulfate, which was then poured into an initiator spray container.
Fixing the carbon cloth on a conveying system, wherein the speed of the conveying belt is 2.5 cm/s; soaking the carbon cloth in aniline monomer for 10min, and spraying initiator at a spraying speed of 2.0 ml/s; the distance between the positive and negative flat plate electrodes is 5cm, and the applied direct current high voltage is 5 kV; the residence time of the high-voltage electric field polymerization system is 30 min; and then conveying the carbon cloth to a low-temperature reaction system, ensuring that the temperature of the carbon cloth does not exceed 0 ℃, and continuing to react for 300 min. And cleaning the conveyed carbon cloth with deionized water to obtain the polyaniline nano-cluster/carbon cloth composite material. Meanwhile, the modulus of the original commercial carbon cloth is 0.15MPa, the modulus of the polyaniline/carbon cloth composite material after the reaction is still 0.15MPa, and the initial excellent mechanical property of the polyaniline/carbon cloth composite material is reserved.
The appearance of the polyaniline nano-fiber is observed by a scanning electron microscope, as shown in figure 2, the polyaniline nano-fiber has the diameter of about 30nm to 50nm and the length of about 500nm to 1 mu m, is in a nano-cluster structure and has no obvious agglomeration phenomenon. The prepared polyaniline nanocluster/carbon cloth composite material is cut into a sheet shape of 1cm multiplied by 2cm, electric wires are connected to two ends of the sheet shape to assemble a gas-sensitive sensing element, gas sensitivity test is carried out on formaldehyde gas with the concentration of 300ppb, the obtained gas response curve is shown in figure 3, and the fact that after the polyaniline nanocluster is placed in the formaldehyde gas, the resistance is rapidly increased, and after the polyaniline nanocluster is removed, the fiber resistance is rapidly reduced. The resistance can be basically recovered to the initial value which is not put into formaldehyde gas in five cycles, excellent recovery performance is shown, the change of the relative resistance value is close to zero, and the recovery time and the corresponding time required by each cycle are basically the same and are about 40s, which indicates that the composite material has good gas sensing response behavior.
Example 3
46.565g (0.5mol) of aniline is weighed and added into 5L of 0.1M hydrochloric acid aqueous solution to prepare an acid solution of aniline, and the acid solution is injected into an aniline monomer soaking container; 99.965g (0.25mol) of ferric sulfate and 57.05g (0.25mol) of ammonium persulfate are weighed and added into 5L of 1M hydrochloric acid aqueous solution containing 1 wt% of camphorsulfonic acid to prepare an acid solution of a compounded oxidant, and then the acid solution is injected into an initiator spraying container.
Fixing the carbon paper on a conveying system, wherein the speed of the conveying belt is 2.5 cm/s; soaking carbon paper in aniline monomer for 120min, and spraying initiator at a spraying speed of 0.1 ml/s; the distance between the positive and negative flat plate electrodes is 20cm, and the applied direct current high voltage is 50 kV; the residence time of the high-voltage electric field polymerization system is 240 min; and then conveying the carbon paper to a low-temperature reaction system, ensuring that the temperature of the carbon paper does not exceed 10 ℃, and continuing to react for 120 min. And cleaning the conveyed carbon paper with deionized water to obtain the polyaniline nano-cluster/carbon paper composite material.
The morphology of the carbon paper is observed by a scanning electron microscope, and as shown in fig. 4, under the action of a high-voltage electric field, aniline is subjected to polymerization growth along the vertical direction of the carbon paper to form an ordered and dense nano-particle structure. Cutting the prepared polyaniline nano-cluster/carbon paper composite material into a sheet shape of 1cm multiplied by 2cm, placing the sheet in a potassium dichromate aqueous solution with the initial concentration of 100mg/L for chromium ion adsorption for 360min, wherein the adsorption kinetics curve and the color change conditions of the potassium dichromate aqueous solution before and after adsorption are shown in figure 5; as can be seen from the curve, the composite material can be rapidly adsorbed to 180mg/g within 45min and reaches equilibrium of 195mg/g within 80min, and the adsorption efficiency and the adsorption capacity are high.
Example 4
465.65g (5mol) aniline is weighed and added into 5L 1M perchloric acid and sulfuric acid (1:1) water solution to prepare aniline acid solution, and the aniline acid solution is injected into an aniline monomer infiltration container; 811.02g (5mol) of ferric chloride was weighed into 5L of 1M hydrochloric acid aqueous solution to prepare an acidic solution of ferric chloride, which was then poured into an initiator spray container.
Fixing the graphene film on a conveying system, wherein the speed of the conveying belt is 1.0 cm/s; soaking the graphene film in aniline monomer for 30min, and then spraying an initiator at a spraying speed of 1.0 ml/s; the distance between the positive and negative flat plate electrodes is 10cm, and the applied direct current high voltage is 20 kV; the residence time of the high-voltage electric field polymerization system is 60 min; and then conveying the graphene film to a low-temperature reaction system, ensuring that the temperature of the graphene film is not more than 0 ℃, and continuing to react for 300 min. And cleaning the conveyed graphene film by using deionized water to obtain the polyaniline nano-cluster/graphene film composite material.
The morphology of the polyaniline film is observed by a scanning electron microscope, as shown in fig. 6, polyaniline is uniformly distributed on the surface of the graphene film, a highly vertically ordered polyaniline nanocluster array is formed, and the diameter of the nanocluster is 30-40 nm. The prepared polyaniline nanocluster/graphene composite material is cut into a sheet shape of 2cm × 2cm, and a cyclic voltammetry curve measured in a 0.5M sulfuric acid solution by adopting a three-electrode system is shown in fig. 7. Three pairs of oxidation-reduction peaks can be observed on the curve, corresponding to the transition among various oxidation states of polyaniline, and the area specific capacitance of the polyaniline reaches 1026mF cm under the condition of 10mV/s-2Higher than many research levels at present, which shows that the electrochemical performance is good; meanwhile, under the conditions of stretching, folding and twisting, the shape and size of the cyclic voltammetry curve are basically unchanged, so that the composite fabric electrode retains the excellent flexibility of the graphene film, can be wound, folded, compressed and the like, and can be used for assembling a high-performance flexible supercapacitor.
Claims (10)
1. A continuous preparation method of polyaniline nanoclusters comprises the following steps:
soaking the flexible conductive substrate in an aniline solution, spraying an initiator solution on two sides, carrying out polymerization reaction in a high-voltage electric field, continuing reaction in a low-temperature environment, and finally washing and drying to obtain a polyaniline nanocluster;
the method specifically comprises the following steps: the flexible conductive substrate is soaked in the aniline monomer soaking system (2) through the conveying system (1) and then conveyed to the initiator spraying system (3) for double-sided spraying; timely transmitting the mixture to a high-voltage electric field polymerization system (4) for reaction, and then continuing the reaction in a low-temperature reaction system (5); the whole device adjusts the temperature through a water cooling system (6) and a temperature controller (7).
2. The production method according to claim 1, wherein the flexible conductive substrate is conveyed by a conveying system to be continuously produced; the flexible conductive substrate is one of carbon cloth, carbon paper and graphene film.
3. The preparation method according to claim 1, wherein the soaking time is 10-120 min, and the spraying rate is 0.01-2 ml/s.
4. The preparation method according to claim 1, wherein the aniline solution is obtained by dissolving aniline in an acidic medium, the concentration of the aniline solution is 0.1-3.0M, and the acidic medium is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid and perchloric acid.
5. The preparation method according to claim 1, wherein the initiator solution is obtained by dissolving an initiator in an acid medium, wherein the concentration of the initiator solution is 0.01-4.0M; the acid medium is one or more of hydrochloric acid, sulfuric acid, phosphoric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid and perchloric acid; the initiator is one or more of persulfates, dichromate, transition metal salts, peroxides and potassium permanganate.
6. The preparation method according to claim 1, wherein the parameters of the polymerization reaction carried out in the high-voltage electric field are as follows: the high-voltage electric field is a flat electric field, the distance between the positive flat electrode and the negative flat electrode is 5-20 cm, the flexible conductive base material is located in the center of the flat electrodes, the applied direct-current high voltage is 5-50 kV, and the polymerization reaction time is 30-240 min.
7. The preparation method according to claim 1, wherein the continuous reaction in the low-temperature environment is: the temperature is 0-10 ℃, and the reaction time is 180-330 min.
8. A polyaniline nanocluster prepared by the method of claim 1, wherein: and a polyaniline nano-cluster is grown on the flexible conductive base material.
9. Use of the polyaniline nanocluster of claim 8 in the fields of energy storage materials, sensing materials, electromagnetic shielding materials, antistatic materials, and conductive composites.
10. A continuous preparation device of polyaniline nanoclusters is characterized in that: the preparation device is internally provided with an aniline monomer infiltration system (2), an initiator spraying system (3), a high-voltage electric field polymerization system (4), a low-temperature reaction system (5) and a conveying system (1) in sequence, flexible conductive base materials sequentially pass through the aniline monomer infiltration system (2), the initiator spraying system (3), the high-voltage electric field polymerization system (4) and the low-temperature reaction system (5) under the traction of the conveying system (1), the preparation device is internally controlled in temperature through a circulating water cooling system (6), and the circulating water cooling system (6) is connected with a temperature controller (7).
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