Continuous production of binary conductive polymer composite nanofibers

Abstract

This invention provides a continuous preparation apparatus and method for binary conductive polymer composite nanofibers. A dopant-containing aniline monomer solution and initiator solution, and a dopant-containing thiophene monomer solution and initiator solution are respectively injected into corresponding containers. Under gravity, the aniline monomer solution and its initiator solution flow into the main pipe through branch pipes, where they mix and polymerize to form polyaniline nanofibers. Subsequently, they continue to flow in the main pipe and mix with the thiophene solution and its initiator solution. Thiophene undergoes in-situ chemical oxidative polymerization on the surface of the polyaniline nanofibers, generating polyaniline / polythiophene composite nanofibers. After washing and drying, the polyaniline / polythiophene composite nanofibers are obtained. The entire flow and mixing process of this invention is achieved by gravity, eliminating the need for mixing and stirring devices and pumps; this avoids clogging of the solution during polymerization and greatly improves production efficiency.

Description

Technical Field

[0001] This invention belongs to the field of preparation of nano-conductive composite fiber materials, and specifically relates to a continuous preparation apparatus and method for binary conductive polymer composite nanofibers. Background Technology

[0002] Supercapacitors, as important energy storage devices, have high research and application value. Electrode materials, as a key component, are crucial indicators determining their performance. The development of flexible wearable electronics, in particular, has created unprecedented market prospects for flexible electrode materials. Conductive polymer nanofibers, as flexible electrode materials, possess highly ordered structures that significantly improve carrier mobility, resulting in superior performance. Among numerous conductive polymers, polyaniline and polythiophene offer advantages such as simple synthesis methods, high conductivity, and reversible doping / dedoping processes. Combined with the high surface area and high order of nanofiber structures, their energy storage performance is greatly improved, demonstrating significant development potential. Organically combining polyaniline and polythiophene to prepare polyaniline / polythiophene composite nanofibers can create favorable conditions for the development of high-energy-storage-performance electrode materials. Currently, the preparation of polyaniline and polythiophene mainly includes electrochemical methods and chemical oxidation methods [CN108395556A, CN111635505B]. Electrochemical methods polymerize monomers directly on inert electrodes under the influence of an electric field. This method requires expensive electrochemical equipment, and yield is limited by the electrode area, making mass production difficult. In contrast, chemical methods do not require expensive equipment and are characterized by low cost, simple operation, and ease of large-scale production. These methods mainly include template-based and template-free methods. Template-based methods require a template to allow the monomers to polymerize within the template's pores. The template is then removed to obtain the polymer material. This method is cumbersome, and template removal may damage the polymer's internal structure, limiting performance improvements [CN100497761C, CN103665376B, CN114783790A]. Template-free methods, which do not require the use of templates, mainly include interfacial polymerization [CN101016660A], emulsion polymerization [CN102060993A], and flow polymerization [CN110215892A]. However, these methods also have certain limitations, such as the need for organic solvents and emulsifiers, cumbersome post-processing, and the need for power equipment. For polyaniline / polythiophene composites, the currently reported preparation methods mainly employ template methods, and are achieved through a two-step process. For example, patent CN103224704B uses fibrous attapulgite as a template to first prepare an attapulgite / polyaniline / polythiophene ternary composite material, and then dissolves the attapulgite with mixed acid to obtain polyaniline / polythiophene composite nanotubes; patent CN107794600A uses nanocellulose as a hard template and methyl orange and sodium dodecylbenzenesulfonate as soft templates to prepare nanocellulose / polythiophene / polyaniline composite nanofibers, and then dissolves the nanocellulose with an ionic liquid to obtain polythiophene / polyaniline composite nanotubes. These methods all struggle to avoid the damage to the material structure caused by template removal, thus limiting the improvement of conductivity and energy storage performance, and making continuous production difficult. Summary of the Invention

[0003] The technical problem to be solved by this invention is to provide a one-step continuous preparation apparatus and method for binary conductive polymer composite nanofibers. First, an aniline monomer solution and an aniline monomer initiator solution are mixed and polymerized in a main pipeline to generate polyaniline nanofibers. Subsequently, the solution containing the polyaniline nanofibers continues to flow in the main pipeline and combines with a thiophene solution and its initiator solution, causing thiophene to undergo in-situ chemical oxidative polymerization on the surface of the polyaniline nanofibers, thereby generating polyaniline / polythiophene composite nanofibers. After washing and drying, the final product is obtained. This invention's preparation method is low-cost, simple to operate, and allows for controllable reactions. It eliminates the need for expensive equipment, templates, and organic solvents, avoiding cumbersome post-processing steps, greatly improving production efficiency, and enabling real-time acquisition of the composite material and its pure components. It is an effective approach for the large-scale production of polyaniline / polythiophene composite nanofibers.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] This invention provides a continuous preparation device for binary conductive polymer composite nanofibers, comprising a monomer container A, an initiator container B, a monomer container C, and an initiator container D. Monomer container A and initiator container B are positioned at the same height. Monomer container C and initiator container D are respectively positioned below monomer container A and initiator container B at the same height. The outlets of monomer container A, initiator container B, monomer container C, and initiator container D are respectively connected to a main pipeline via branch pipes. The main pipeline is provided with reaction container I and reaction container II sequentially from top to bottom. The outlet of reaction container II is connected to a collection container.

[0006] Preferably, the outlets of monomer container A and initiator container B are connected to the main pipeline via branch pipes and to the inlet of reaction container I; the outlets of monomer container C and initiator container D are connected to the main pipeline via branch pipes and to the inlet of reaction container II; and throttling valves are provided at the outlets of monomer container A, initiator container B, monomer container C, initiator container D, reaction container I, and reaction container II.

[0007] Preferably, the height of the monomer container A, initiator container B, monomer container C, and initiator container D is 0.1~2 m, the inner diameter of the main pipeline is 0.001~0.5 m, and the total length is 1~5 m. The total length of the main pipeline refers to the total length of the main pipeline from the connection point of the branch pipelines of monomer container A and initiator container B to the collection container.

[0008] Preferably, the volume ratio of reaction vessel I to reaction vessel II is 1:(0.1~8). The regulating valves at the outlets of reaction vessel I and reaction vessel II can control the flow rate of the solution in the main pipeline, and the volume ratio of the two vessels respectively regulates the relative flow polymerization time of aniline and thiophene.

[0009] Preferably, this device can be used to prepare single or composite conductive polymer nanofiber materials for oxidative polymerization reactions. The continuous preparation of the device of the present invention includes, but is not limited to, polyaniline / polythiophene composite nanofibers; the container and pipe are made of acid and alkali resistant materials such as polytetrafluoroethylene resin, phenolic resin or organosilicon monomer resin.

[0010] This invention also provides a continuous preparation method for binary conductive polymer composite nanofibers, the steps of which are as follows:

[0011] (1) The aniline monomer solution containing dopant and the aniline monomer initiator solution are injected into monomer container A and initiator container B respectively. The thiophene monomer solution containing dopant and the thiophene monomer initiator solution are injected into monomer container C and initiator container D respectively. The solution level is adjusted. Under the control of the throttle valve at the outlet of monomer container A and initiator container B, the aniline monomer solution and its initiator solution are made to flow into the main pipeline through the branch pipe by the solution pressure. The aniline monomer solution and the initiator solution are mixed and flowed in the main pipeline to generate polyaniline nanofibers, which flow into reaction container I to continue to react and generate polyaniline nanofibers.

[0012] (2) Under the control of the throttle valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mix with the thiophene solution and its initiator solution. The thiophene undergoes in-situ chemical oxidation polymerization on the surface of the polyaniline nanofibers to generate polyaniline / polythiophene composite nanofibers, which flow into reaction container II to generate a large amount of products. The flow rate of the solution is controlled by the throttle valves at the outlets of reaction container I and reaction container II.

[0013] (3) After the reaction is complete, the product in reaction vessel II is collected in the collection container, and then washed and dried to obtain polyaniline / polythiophene composite nanofibers.

[0014] Preferably, the liquid levels of the doped aniline monomer solution and aniline monomer initiator solution in monomer container A and initiator container B are 0.07~1.5 m, with a height ratio of 1:(0.5~3), and the molar ratio of aniline monomer to aniline monomer initiator is 1:(0.2~8). The liquid levels of the doped thiophene monomer solution and thiophene monomer initiator solution in monomer container C and initiator container D are 0.07~1.5 m, with a height ratio of 1:(0.5~3), and the molar ratio of thiophene monomer to thiophene monomer initiator is 1:(0.2~8).

[0015] Preferably, the molar concentrations of the aniline monomer solution and the thiophene monomer solution are 0.02–2 mol / L, and the molar ratio of aniline monomer to thiophene monomer is 1:(0.1–10).

[0016] Preferably, the dopant is a single or compound dopant such as hydrochloric acid, sulfuric acid, nitric acid, sulfosalicylic acid, saturated fatty acid, dodecylbenzenesulfonic acid, etc., with a molar concentration of 0.1~3 mol / L.

[0017] Preferably, the aniline monomer initiator is a single or compound initiator selected from ammonium persulfate, ferric chloride, hydrogen peroxide, and potassium dichromate, and the thiophene monomer initiator is a compound initiator composed of ammonium persulfate, ferric chloride, hydrogen peroxide, and potassium dichromate.

[0018] The synthesis mechanism of this invention is as follows: First, an aniline monomer solution and its initiator solution are introduced into the same reaction tube by gravity. They are mixed and undergo flow polymerization within the tube. Due to the confined space within the reaction tube, polyaniline grows in an oriented manner, forming polyaniline nanofibers, which continue to flow. When the solution containing polyaniline nanofibers combines with a thiophene solution and its initiator solution, intermolecular forces cause thiophene molecules to be adsorbed onto the polyaniline nanofibers and polymerize on their surface, ultimately forming polyaniline / polythiophene composite nanofibers. This invention not only enables the one-step continuous preparation of polyaniline / polythiophene composite nanofibers but also effectively promotes polymer orientation growth, making it an effective method for preparing high-energy-storage electrode materials.

[0019] The beneficial effects of this invention are:

[0020] (1) The present invention has significant features compared with the existing methods for preparing conductive polyaniline / polythiophene composite materials. The invention can prepare polyaniline / polythiophene composite nanofiber materials, which have a higher aspect ratio than polyaniline / polythiophene composite nanotubes. Flow polymerization helps polymer molecules to align, which greatly improves the structural order and regularity. All of these will greatly improve the electron transport rate and effectively improve the energy storage performance of the material.

[0021] (2) This invention enables one-step continuous preparation of polyaniline / polythiophene composite materials. The polymerization process is carried out in the aqueous phase without any template or organic solvent, making the operation simple and eliminating the need for complicated post-processing steps. It uses only gravity as the power source, eliminating the need for any power equipment or stirring equipment, resulting in low cost. At the same time, due to the presence of the reaction vessel, this invention can effectively prevent the reaction products generated during the polymerization process from causing blockages in the pipeline, thus promptly curbing secondary growth and ensuring the uniformity and repeatability of the material. It can simultaneously obtain the composite material and its pure components. The one-dimensional preparation process in space facilitates real-time monitoring of each polymerization growth point, which is more conducive to mechanism research. Continuous preparation can effectively improve production efficiency and is suitable for large-scale industrial production.

[0022] (3) The polyaniline / polythiophene composite fiber prepared by the present invention has a regular morphology, orderly structure and good dispersibility; it can be applied to many fields such as energy storage and conversion materials, conductive materials, sensing materials, antistatic materials, anti-corrosion materials, electromagnetic shielding materials, and adsorption materials. Attached Figure Description

[0023] Figure 1 A schematic diagram of the apparatus for preparing polyaniline / polypyrrole binary composite nanofibers;

[0024] Figure 2 This is a transmission electron microscope (TEM) image of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 1 of this invention.

[0025] Figure 3 The cyclic voltammetry curves of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 2 of this invention are shown at a scan rate of 5 mV / s in 0.5 mol / L sodium sulfate electrolyte.

[0026] Figure 4 This is a scanning electron microscope image of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 3 of the present invention.

[0027] Figure 5 The constant current charge-discharge curves of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 4 of this invention at a scan rate of 2 A / g in 0.5 mol / L sodium sulfate electrolyte are shown.

[0028] Figure 6 This is a scanning electron microscope image of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 5 of the present invention.

[0029] Figure 7 The image shows the AC impedance curve of the polyaniline / polypyrrole binary composite nanofibers synthesized in Example 6 of this invention in 0.5 mol / L sodium sulfate electrolyte. Detailed Implementation

[0030] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0031] Example 1

[0032] like Figure 1 As shown, the continuous preparation device for binary conductive polymer composite nanofibers of the present invention includes a monomer container A, an initiator container B, a monomer container C, and an initiator container D. The monomer container A and the initiator container B are arranged at the same height. The monomer container C and the initiator container D are respectively arranged below the monomer container A and the initiator container B and are located at the same height. The outlets of the monomer container A, the initiator container B, the monomer container C, and the initiator container D are respectively connected to the main pipeline via branch pipes. The main pipeline is provided with a reaction container I and a reaction container II from top to bottom. The outlet of the reaction container II is connected to a collection container.

[0033] The outlets of monomer container A and initiator container B are connected to the main pipeline via branch pipes and are also connected to the inlet of reaction container I. The outlets of monomer container C and initiator container D are connected to the main pipeline via branch pipes and are also connected to the inlet of reaction container II. Throttling valves are provided at the outlets of monomer container A, initiator container B, monomer container C, initiator container D, reaction container I, and reaction container II.

[0034] The monomer container A, initiator container B, monomer container C, and initiator container D have a height of 0.1 m; the length from the connection point of the branch pipes of monomer container A and initiator container B on the main pipeline to the connection point of the collection container is 1 m, and the inner diameter is 0.001 m; the volume ratio of reaction container I to reaction container II is 1:0.1.

[0035] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0036] (1) Accurately weigh a certain amount of aniline and ammonium persulfate, and add them to a 0.1 mol / L hydrochloric acid solution to prepare a 0.02 mol / L aniline monomer solution and a 0.004 mol / L ammonium persulfate solution. Then, inject them into the monomer container A and the initiator container B respectively, and adjust the liquid level of the aniline monomer to 0.07 m and the liquid level of the ammonium persulfate to 0.35 m. Then, accurately weigh a certain amount of thiophene, ammonium persulfate and ferric chloride, and add them to a 0.1 mol / L hydrochloric acid solution to prepare a 0.02 mol / L thiophene monomer solution and a 0.004 mol / L ammonium persulfate and ferric chloride mixture. Then, inject them into the monomer container C and the initiator container D respectively, and adjust the liquid level of the thiophene monomer to 0.07 m and the liquid level of the ammonium persulfate to 0.35 m.

[0037] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction vessel I; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction vessel II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers with a diameter between 20 and 70 nm and a length between 100 and 550 nm (see...). Figure 2 ).

[0038] Example 2

[0039] In this embodiment of the continuous preparation device for binary conductive polymer composite nanofibers, the dimensions and height of monomer container A, initiator container B, monomer container C, and initiator container D4 are 0.5 m; the length from the connection point of the branch pipe of monomer container A and initiator container B to the connection point of the collection container on the main pipeline is 2 m, and the inner diameter is 0.01 m; the volume ratio of reaction container I to reaction container II is 1:1, and other implementation methods are the same as in Embodiment 1.

[0040] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0041] (1) Accurately weigh a certain amount of aniline, hydrogen peroxide and ferric chloride, and add them to a 0.5 mol / L sulfuric acid solution to prepare a 0.1 mol / L aniline monomer solution and a 0.8 mol / L hydrogen peroxide and ferric chloride mixture. These solutions are then injected into monomer container A and initiator container B, respectively. The liquid level of the aniline monomer is adjusted to 0.1 m and the liquid level of the hydrogen peroxide is adjusted to 0.3 m. Then, accurately weigh a certain amount of thiophene, hydrogen peroxide and ferric chloride, and add them to a 0.5 mol / L sulfuric acid solution to prepare a 0.2 mol / L thiophene monomer solution and a 1.6 mol / L hydrogen peroxide and ferric chloride mixture. These solutions are then injected into monomer container C and initiator container D, respectively. The liquid level of the thiophene monomer is adjusted to 0.1 m and the liquid level of the hydrogen peroxide is adjusted to 0.3 m.

[0042] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction container I; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction container II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers. Figure 3 Cyclic voltammetry curves of the composite nanofiber as an electrode were obtained at a scan rate of 5 mV / s in 0.5 mol / L sodium sulfate electrolyte, and its specific capacitance was calculated to be 406.5 F / g.

[0043] Example 3

[0044] In this embodiment of the continuous preparation apparatus for binary conductive polymer composite nanofibers, the dimensions and height of monomer container A, initiator container B, monomer container C, and initiator container D are 0.8 m; the length from the connection point of the branch pipes of monomer container A and initiator container B to the connection point of the collection container on the main pipeline is 2.5 m, and the inner diameter is 0.05 m; the volume ratio of reaction container I to reaction container II is 1:1.5, and other implementation methods are the same as in Embodiment 1.

[0045] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0046] (1) Accurately weigh a certain amount of aniline, ferric chloride and ammonium persulfate, and add them to a mixture of 1 mol / L sulfosalicylic acid and hydrochloric acid to prepare a 0.2 mol / L aniline monomer solution and a 0.4 mol / L ferric chloride and ammonium persulfate mixture. Then inject them into monomer container A and initiator container B respectively, and adjust the liquid level of aniline monomer to 0.2 m and the liquid level of ferric chloride to 0.2 m. Then accurately weigh a certain amount of thiophene, ferric chloride and ammonium persulfate, and add them to a mixture of 1 mol / L sulfosalicylic acid and hydrochloric acid to prepare a 2 mol / L thiophene monomer solution and a 0.4 mol / L ferric chloride and ammonium persulfate mixture. Then inject them into monomer container C and initiator container D respectively, and adjust the liquid level of thiophene monomer to 0.2 m and the liquid level of ferric chloride to 0.2 m.

[0047] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction container I6; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction container II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers with a diameter between 30 and 60 nm and a length between 120 and 500 nm (see...). Figure 4 ).

[0048] Example 4

[0049] In this embodiment of the continuous preparation apparatus for binary conductive polymer composite nanofibers, the dimensions and height of monomer container A, initiator container B, monomer container C, and initiator container D are 1 m; the length from the connection point of the branch pipe of monomer container A and initiator container B to the connection point of the collection container on the main pipeline is 3 m, and the inner diameter is 0.1 m; the volume ratio of reaction container I to reaction container II is 1:5, and other implementation methods are the same as in Embodiment 1.

[0050] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0051] (1) Accurately weigh a certain amount of aniline and potassium dichromate, and add them to a mixture of 1.5 mol / L nitric acid and hydrochloric acid to prepare a 1 mol / L aniline monomer solution and a 1 mol / L potassium dichromate solution. Then, inject them into monomer container A and initiator container B respectively, and adjust the liquid level of aniline monomer to 0.5 m and the liquid level of potassium dichromate to 1 m. Then, accurately weigh a certain amount of thiophene, potassium dichromate and ferric chloride, and add them to a mixture of 1.5 mol / L nitric acid and hydrochloric acid to prepare a 0.5 mol / L thiophene monomer solution and a 1 mol / L potassium dichromate and ferric chloride mixture. Then, inject them into monomer container C and initiator container D respectively, and adjust the liquid level of thiophene monomer to 0.5 m and the liquid level of potassium dichromate to 1 m.

[0052] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction container I; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction container II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers. Figure 5 The constant current charge-discharge curves of the composite nanofiber as an electrode were obtained under a current density of 2 A / g in a 0.5 mol / L sodium sulfate electrolyte, and its specific capacitance was calculated to be 371.8 F / g.

[0053] Example 5

[0054] In this embodiment of the continuous preparation apparatus for binary conductive polymer composite nanofibers, the dimensions and height of monomer container A, initiator container B, monomer container C, and initiator container D are 1.5 m; the length from the connection point of the branch pipes of monomer container A and initiator container B to the connection point of the collection container on the main pipeline is 4 m, and the inner diameter is 0.4 m; the volume ratio of reaction container I to reaction container II is 1:3, and other implementation methods are the same as in Embodiment 1.

[0055] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0056] (1) Accurately weigh a certain amount of aniline and hydrogen peroxide, and add them to a mixed solution of 3 mol / L dodecylbenzenesulfonic acid and hydrochloric acid to prepare a 1.5 mol / L aniline monomer solution and a 1.2 mol / L hydrogen peroxide solution. Then, inject them into monomer container A and initiator container B respectively, and adjust the liquid level of aniline monomer to 1.2 m and the liquid level of hydrogen peroxide to 0.8 m. Then, accurately weigh a certain amount of thiophene, hydrogen peroxide and ferric chloride, and add them to a mixed solution of 3 mol / L dodecylbenzenesulfonic acid and hydrochloric acid to prepare a 1.8 mol / L thiophene monomer solution and a 1.2 mol / L hydrogen peroxide and ferric chloride mixture. Then, inject them into monomer container C and initiator container D respectively, and adjust the liquid level of thiophene monomer to 1.2 m and the liquid level of hydrogen peroxide to 0.8 m.

[0057] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction container I; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction container II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers with a diameter between 40 and 80 nm and a length between 150 and 600 nm (see...). Figure 6 ).

[0058] Example 6

[0059] In this embodiment of the continuous preparation apparatus for binary conductive polymer composite nanofibers, the dimensions and height of monomer container A, initiator container B, monomer container C, and initiator container D are 2 m; the length from the connection point of the branch pipe of monomer container A and initiator container B to the connection point of the collection container on the main pipeline is 5 m, and the inner diameter is 0.5 m; the volume ratio of reaction container I to reaction container II is 1:8, and other implementation methods are the same as in Embodiment 1.

[0060] The method for preparing binary conductive polymer composite nanofibers using the above-described continuous preparation apparatus in this embodiment is as follows:

[0061] (1) Accurately weigh a certain amount of aniline and ammonium persulfate, and add them to a 2 mol / L nitric acid solution to prepare a 2 mol / L aniline monomer solution and a 1.6 mol / L ammonium persulfate solution. Then, inject them into the monomer container A and the initiator container B respectively, and adjust the liquid level of the aniline monomer to 1.5 m and the liquid level of the ammonium persulfate to 1 m. Then, accurately weigh a certain amount of thiophene, ammonium persulfate and ferric chloride, and add them to a 2 mol / L nitric acid solution to prepare a 1.2 mol / L thiophene monomer solution and a 1.6 mol / L mixture of ammonium persulfate and ferric chloride. Then, inject them into the monomer container C and the initiator container D respectively, and adjust the liquid level of the thiophene monomer to 1.5 m and the liquid level of the ammonium persulfate to 1 m.

[0062] (2) Under the control of the throttling valves at the bottom outlets of monomer container A and initiator container B, the aniline monomer solution and the aniline monomer initiator solution are mixed and polymerized in the main pipeline and flow into reaction container I; under the control of the throttling valves at the bottom outlets of monomer container C and initiator container D, the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes and reacts with the thiophene solution and its initiator solution, and then flows into reaction container II. The product is washed, filtered, and dried to obtain polyaniline / polythiophene composite nanofibers. Figure 7 The AC impedance curves of the composite nanofibers as electrodes in 0.5 mol / L sodium sulfate electrolyte are shown.

Claims

1. A continuous preparation apparatus for binary conductive polymer composite nanofibers, characterized in that: The container includes a monomer container A (1), an initiator container B (2), a monomer container C (3), and an initiator container D (4). The monomer container A (1) and the initiator container B (2) are set at the same height. The monomer container C (3) and the initiator container D (4) are set below the monomer container A (1) and the initiator container B (2) and at the same height. The outlets of the monomer container A (1), the initiator container B (2), the monomer container C (3), and the initiator container D (4) are connected to the main pipeline through branch pipes. The main pipeline is provided with reaction container I (6) and reaction container II (7) from top to bottom. The outlet of reaction container II (7) is connected to the collection container (8). The dimensions of the monomer container A (1), initiator container B (2), monomer container C (3), and initiator container D (4) are 0.1 ~ 2 m in height, the inner diameter of the main pipeline is 0.001 ~ 0.5 m, and the total length is 1 ~ 5 m.

2. The continuous preparation apparatus for binary conductive polymer composite nanofibers according to claim 1, characterized in that: The outlets of the monomer container A (1) and the initiator container B (2) are connected to the main pipeline via branch pipes and to the inlet of the reaction container I (6). The outlets of the monomer container C (3) and the initiator container D (4) are connected to the main pipeline via branch pipes and to the inlet of the reaction container II (7). Throttling valves (5) are provided at the outlets of the monomer container A (1), the initiator container B (2), the monomer container C (3), the initiator container D (4), the reaction container I (6), and the reaction container II (7).

3. The continuous preparation apparatus for binary conductive polymer composite nanofibers according to claim 1, characterized in that: The volume ratio of reaction vessel I (6) to reaction vessel II (7) is 1:(0.1 ~ 8).

4. The continuous preparation apparatus for binary conductive polymer composite nanofibers according to claim 1, characterized in that: This device can be used to prepare single or composite conductive polymer nanofiber materials by oxidative polymerization reaction. The continuous preparation of the device of the present invention includes, but is not limited to, polyaniline / polythiophene composite nanofibers. The container and pipe are made of acid and alkali resistant materials, including polytetrafluoroethylene resin, phenolic resin or organosilicon monomer resin.

5. A method for preparing binary conductive polymer composite nanofibers using the continuous preparation apparatus according to any one of claims 1-3, characterized in that... Includes the following steps: (1) The dopant-containing aniline monomer solution and aniline monomer initiator solution are injected into monomer container A (1) and initiator container B (2) respectively. The dopant-containing thiophene monomer solution and thiophene monomer initiator solution are injected into monomer container C (3) and initiator container D (4) respectively. The solution level is adjusted. Under the control of the throttle valve at the outlet of monomer container A (1) and initiator container B (2), the aniline monomer solution and its initiator solution are made to flow into the main pipeline through the branch pipe by the solution pressure. The aniline monomer solution and the initiator solution are mixed and flowed in the main pipeline to generate polyaniline nanofibers, which flow into reaction container I (6) to continue the reaction to generate polyaniline nanofibers. (2) Under the control of the throttle valves at the outlets of the monomer container C (3) and the initiator container D (4), the solution containing polyaniline nanofibers continues to flow in the main pipeline and mixes with the thiophene solution and its initiator solution. The thiophene undergoes in-situ chemical oxidation polymerization on the surface of the polyaniline nanofibers to generate polyaniline / polythiophene composite nanofibers, which flow into the reaction container II (7) to generate a large amount of products. The flow rate of the solution is controlled by the throttle valves at the outlets of the reaction container I (6) and the reaction container II (7). (3) After the reaction is complete, the product in reaction vessel II (7) is collected in the collection container, and then washed and dried to obtain polyaniline / polythiophene composite nanofibers; The liquid levels of the doped aniline monomer solution and aniline monomer initiator solution in monomer container A (1) and initiator container B (2) are 0.07 ~ 1.5 m, with a height ratio of 1:(0.5 ~ 3), and the molar ratio of aniline monomer to aniline monomer initiator is 1:(0.2 ~ 8). The liquid levels of the doped thiophene monomer solution and thiophene monomer initiator solution in monomer container C (3) and initiator container D (4) are 0.07 ~ 1.5 m, with a height ratio of 1:(0.5 ~ 3), and the molar ratio of thiophene monomer to thiophene monomer initiator is 1:(0.2 ~ 8).

6. The method for preparing binary conductive polymer composite nanofibers according to claim 5, characterized in that: The molar concentrations of the aniline monomer solution and the thiophene monomer solution are 0.02–2 mol / L, and the molar ratio of aniline monomer to thiophene monomer is 1:(0.1–10).

7. The method for preparing binary conductive polymer composite nanofibers according to claim 5, characterized in that: The dopant is a single or compound dopant selected from hydrochloric acid, sulfuric acid, nitric acid, sulfosalicylic acid, saturated fatty acid, and dodecylbenzenesulfonic acid, with a molar concentration of 0.1~3 mol / L.

8. The method for preparing binary conductive polymer composite nanofibers according to claim 5, characterized in that: The aniline monomer initiator is a single or compound initiator selected from ammonium persulfate, ferric chloride, hydrogen peroxide, and potassium dichromate, and the thiophene monomer initiator is a compound initiator composed of ammonium persulfate, ferric chloride, hydrogen peroxide, and potassium dichromate.

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