An ordered conductive polymer composite material, its preparation method and application

Abstract

The present invention discloses an ordered conductive polymer composite material, a preparation method thereof, and an application. In a three-electrode system, a mixed solution containing one or more polymer monomers or a polymer monomer and an organic polymer resin monomer is used as an electrolyte, and an ordered array of nanowires is prepared by electrocatalytic self-growth, enabling doping and compounding of different conductive polymers and conductive polymers with organic polymers. The nanowires obtained by the present invention have a uniform diameter, adjustable length, and can achieve the compounding of conductive and proton conduction functions. The preparation process of this method is simple, avoiding the steps of traditional nanowire array preparation that require transition metal catalysis and transfer printing. It has good repeatability, stable performance, and strong compounding ability. The ordered array of composite nanowires has great application prospects in supercapacitors, ordered electrode carriers, solar cells, etc.

Description

Technical Field

[0001] The present invention relates to a conductive polymer composite material, a preparation method thereof, and an application, namely a conductive polymer composite material based on an ordered nanowire array and a preparation method thereof, belonging to the fields of nanomaterials and electrochemical synthesis. Background Art

[0002] Conductive polymer materials have attracted wide attention due to their low cost, the improvement of electron delocalization by their conjugated structure, high conductivity, and electrochemical redox reversibility. Such materials also have advantages such as high capacity, short charge and discharge time, environmental friendliness, and good safety. Therefore, conductive polymer electrode materials have gradually become a research hotspot and are often used as catalysts, electrode carriers, and electrode materials for supercapacitors, etc., all showing good performance. However, when a single conductive polymer material is used as an electrode material, there will be disadvantages such as limited conductivity, low cycle service life, and weak structural stability. In addition, during the electrochemical reaction process, the electrode material not only requires the ability of electron conduction but also requires proton conduction ability, and a single-component conductive polymer material is difficult to meet the usage requirements.

[0003] Patent CN102412016A discloses a preparation method of an ordered micro / nano structure array of a conductive polymer. An ordered thin film of a conductive polymer monomer is obtained by the LB film method, and then an ordered array structure of polymer monomers is obtained on the monomer thin film by an etching method. Finally, an ordered micro / nano structure array of a conductive polymer is obtained by a chemical in-situ polymerization method. In this patent, a series of methods such as an etching method and chemical in-situ polymerization are used to prepare an ordered nanoarray, the process is complex, and the requirements for the preparation environmental conditions are relatively high, which is not conducive to industrial batch production. Summary of the Invention

[0004] The purpose of the present invention is to provide a conductive polymer composite material with an ordered nanostructure and a preparation method thereof. The advantages are that the preparation process of this method is simple, avoiding the steps of traditional nanowire array preparation that require transition metal catalysis and transfer printing, with good repeatability, stable performance, and strong composite properties. This composite nanowire ordered array has great application prospects in supercapacitors, ordered electrode carriers, solar cells, etc.

[0005] The above technical purpose of the present invention is achieved through the following technical solutions: A conductive polymer composite material, the composite material is a composite nanowire ordered array, and the components of the composite nanowire ordered array are one or two or more coupled conductive polymers, or one or two or more coupled conductive polymers and a sulfonic acid group organic polymer resin.

[0006] Further, in the above technical solution, the diameter of the nanowires in the composite nanowire ordered array is 10 - 60 nanometers, and the length of the nanowires is 2 - 10 micrometers; the arrangement of the nanowires is an ordered columnar arrangement or an ordered nanonetwork intertwined arrangement.

[0007] Further, in the above technical solution, the conductive polymer is one or more of polyaniline, polypyrrole, and polythiophene; the sulfonic acid group organic polymer resin is one of perfluorosulfonic acid resin, non-perfluorosulfonic acid resin, or short side chain resin.

[0008] The present invention provides a method for preparing the above conductive polymer composite material, comprising the following steps:

[0009] 1), Prepare a buffer solution;

[0010] 2), Add a conductive polymer monomer, a surfactant, and a monomer solution of the sulfonic acid group organic polymer resin to the buffer solution in step 1), and mix to obtain an electrolyte solution, wherein the concentration of the sulfonic acid group organic polymer resin monomer in the electrolyte solution is 0 - 0.2M;

[0011] 3), Pass an inert gas into the above electrolyte solution, and the gas passed in is nitrogen or argon;

[0012] 4), Keep the electrolyte solution stored at a certain temperature;

[0013] 5), After completing step 4), use a carbon carrier as the working electrode to form a three-electrode system in the electrolyte solution. First, activate it by cyclic voltammetry scanning; after the activation is completed, use the potentiostatic method to control the reaction potential and reaction time, and electrochemically polymerize and self-catalytically grow on the surface of the carrier to prepare a conductive polymer composite material with a nanowire ordered array structure.

[0014] Further, in the above technical solution, in step 1), the specific method for preparing the buffer solution is to take sodium chloride, potassium chloride, sodium dihydrogen phosphate, and disodium hydrogen phosphate with a certain concentration, and mix them to obtain a buffer solution. In the mixed buffer solution, the concentration of sodium chloride is 0.1 - 0.5M, the concentration of potassium chloride is 1 - 5mM, the concentration of sodium dihydrogen phosphate is 1 - 5mM, and the concentration of disodium hydrogen phosphate is 5 - 10mM.

[0015] Further, in the above technical solution, in step 2), the conductive polymer monomer is one or more of aniline, pyrrole, and thiophene, and the total concentration of the conductive polymer monomer in the electrolyte solution is 0.1 - 0.5 M; the sulfonic acid group organic polymer resin is one of perfluorosulfonic acid resin, non-perfluorosulfonic acid resin, or short side chain resin; the surfactant is one or two of sodium α-butene sulfonate, sodium hexadecylnaphthalene sulfonate, and sodium hexadecyl glycerol ether sulfonate, and the concentration of the surfactant in the electrolyte solution is 0.1 - 0.5 M.

[0016] Further, in the above technical solution, in step 3), the flow rate of the introduced gas is 5 - 20 mL / min, and the continuous ventilation time is 45 - 90 min; in step 4), the heat preservation storage is carried out in a constant temperature water bath, the temperature in the constant temperature water bath is 30 - 60 °C, and the heat preservation time is 30 - 60 min.

[0017] Further, in the above technical solution, in step 5), the carbon carrier includes but is not limited to carbon paper, carbon cloth, and carbon fiber materials; the potential range of the activation treatment is from 0 V to 0.5 V, and the number of scanning cycles is 60 - 100; for the potentiostatic method, the reaction potential is set to 0.95 - 1.15 V, and the reaction time is 20 - 50 min.

[0018] Further, in the above technical solution, the diameter and length of the nanowires are regulated by changing reaction conditions such as reaction potential, reaction time, reaction temperature, and the concentration of the surfactant, and the arrangement pattern of the nanowires is controlled to be an ordered columnar arrangement or an ordered nanonetwork intertwined arrangement by regulating the diameter and length of the nanowires.

[0019] The present invention also discloses the application of an ordered array composite nanowire prepared by the above preparation method in supercapacitors, ordered electrode carriers, and solar cells.

[0020] Advantages of the Invention

[0021] 1. The conductive polymer nanowire array composite material of the present invention has an ordered nanostructure, better structural stability, and the composite components are convenient for realizing the synergy of multiple functions. It has many advantages when used as an electrode material or an electrode carrier material, and can effectively realize the orderliness and high efficiency of the electrode reaction process and the mass transfer process. Therefore, the conductive polymer ordered nanowire array can be used to fabricate electrode materials for electrochemical devices such as supercapacitors or ordered electrode carrier materials for other electro-chemical reactors, etc.; the present invention can prepare composite materials of different conductive polymers, which can simultaneously possess the advantages of different conductive polymers and exert their characteristics of high conductivity, high capacity, and fast charge and discharge.

[0022] 2. The method of the present invention can prepare a composite nanowire array material of a conductive polymer and a sulfonic acid resin, coupling the functions of electron transport and proton transport at the same time. When used as an electrode or an electrode carrier, the ordered arrangement structure can not only enhance the mass transport ability during the electrode reaction process, but also improve the electron and proton transport abilities, significantly improving the electrochemical reaction efficiency.

[0023] 3. For the ordered composite nanowire array prepared by the present invention, the diameter of the nanowires is 10 - 60 nanometers, and the length of the nanowires is 2 - 10 micrometers. Using the method described in this patent, the diameter and length of the nanowire array can be controllably adjusted to meet the needs of the microscopic sizes of the vast majority of electrochemical reactions.

[0024] 4. The nanowire array prepared by the method of the present invention can be controlled to present an ordered columnar arrangement structure perpendicular to the growth substrate or an ordered network arrangement structure with the nanowires intertwined with each other, greatly improving the structural stability of the conductive polymer material.

[0025] 5. By controlling the temperature and time conditions of the electrolyte solution, the distribution state and reaction activity of the surfactant and monomer molecules in the solution can be adjusted, which helps to control the subsequent electrochemical deposition process, and jointly with conditions such as potential and time, the specific size of the nanowires can be adjusted. Description of the Drawings

[0026] Figure 1 : Current-time curve of the electrochemical polymerization process of the ordered composite nanowire array;

[0027] Figure 2 : Scanning electron microscope photograph of the ordered composite nanowire array arranged in an ordered columnar structure;

[0028] Figure 3 : Elemental composition of the ordered composite nanowire array;

[0029] Figure 4 : Scanning electron microscope photograph of the ordered composite nanowire array arranged in a nanonetwork intertwined structure;

[0030] Figure 5 : CV test curve of using the ordered composite nanowire array as a supercapacitor electrode material;

[0031] Figure 6 : Polarization curve test of using the ordered composite nanowire array as an ordered electrode carrier of a fuel cell;

[0032] Figure 7 : Cyclic voltammogram curve of a supercapacitor electrode using the composite nanowire array as an electrode material. Detailed Embodiments

[0033] The composite nanowire ordered arrays are prepared by using the preparation method described in this patent, and used as the electrode materials of supercapacitors and the electrode carriers of fuel cell ordered membrane electrodes, and relevant performance tests are carried out.

[0034] Example 1: Preparation of polypyrrole and perfluorosulfonic acid resin composite nanowire arrays arranged in columns

[0035] First, a buffer solution is prepared, in which the concentration of NaCl is 0.2 M, the concentration of KCl is 3 mM, the concentration of sodium dihydrogen phosphate is 2 mM, and the concentration of disodium hydrogen phosphate is 8 mM; pyrrole monomer, surfactant and perfluorosulfonic acid resin solution are added to the above buffer solution, in which the concentration of pyrrole monomer is 0.2 M, the surfactant is sodium hexadecyl naphthalene sulfonate, the concentration of surfactant in the electrolyte solution is 0.4 M, and the concentration of perfluorosulfonic acid resin in the electrolyte solution is 0.1 M. Argon is continuously introduced with a gas flow rate of 10 mL / min for 60 min, and the electrolyte solution is kept in a constant temperature water bath at 50 °C for 45 min. Using carbon cloth as the working electrode, first activate the working electrode, with the scanning potential from 0 V to 0.5 V and scanning 80 cycles. After the activation treatment, set the reaction potential to 1.0 V and the reaction time to 20 min to prepare an ordered nanowire array arranged in columns, and its structure is as Figure 2 shown.

[0036] Example 2: Preparation of polypyrrole and perfluorosulfonic acid resin composite nanowire arrays arranged in an ordered network interweaving pattern

[0037] The difference from Example 1 is that: the concentration of pyrrole monomer in the electrolyte solution is 0.5 M, the reaction potential is 1.1 V, and the reaction time is 50 min to prepare a nanowire array arranged in an ordered network interweaving pattern, and its structure is as Figure 4 shown.

[0038] Figure 1 Shown is the chronoamperometry curve of the electrochemical polymerization process of the composite nanowire ordered array prepared in Example 2, which is divided into four stages: First, the stage of rapid current decline is the charging process of the formation of the electric double layer; in the second stage, monomer molecules adsorb on the electrode surface and the current slowly decreases; in the third stage, the current continuously increases, which is the nucleation process of the polypyrrole ordered nanoarray, and at the same time, the doping of perfluorosulfonic acid resin polyions occurs. As the nuclei grow continuously, the electrochemical polymerization rate increases continuously; the fourth stage is the stable growth stage of the ordered structure composite carrier, and the current is flat.

[0039] As Figure 2 shown, the composite ordered nanowire array prepared in Example 1 is arranged in columns, the diameter of the nanowires is about 50 nm, the length is about 2 μm, the nanowire array is approximately perpendicular to the growth substrate, presenting an ordered arrangement structure.

[0040] Figure 3 As shown, the element composition detection of the composite ordered nanowire array prepared in Example 1, wherein the N element is the characteristic element of polypyrrole, and the S element is the characteristic element of perfluorosulfonic acid resin. According to the detected element composition and distribution results, it is shown that the uniform doping of perfluorosulfonic acid resin polyions is achieved in the polypyrrole ordered nanowire array, forming an ordered structure composite carrier with coupled proton conduction and electron conduction functions.

[0041] like Figure 4 As shown, by changing the control of the reaction conditions, Example 2 prepared a nanowire array with an orderly network interweaving arrangement. The diameter of the nanowires was about 35 nanometers. The nanowires were arranged in an interlaced manner and woven into a network structure. When this structure is used as an electrode carrier material, it can increase the active specific surface area while having good air permeability and structural stability.

[0042] like Figure 5 As shown, the results of cyclic voltammetry scanning tests using the ordered network interwoven nanowire array prepared in Example 2 as the electrode material of the supercapacitor show that the electrode material exhibits good redox properties and can be directly used as an electrode or electrode carrier of the supercapacitor.

[0043] like Figure 6 As shown, the columnar vertically arranged composite ordered nanowire array prepared in Example 1 is used as an electrode carrier, and the oxygen reduction catalyst is loaded as the cathode of the ordered membrane electrode of the fuel cell, and the battery discharge performance curve (polarization curve) obtained by testing. The noble metal platinum loading of the ordered structure electrode is about 6μg / cm 2 (about 1 / 20 of the Pt loading of traditional electrodes. The ultra-low Pt loading electrode based on this ordered structure composite carrier showed excellent battery performance with a maximum power density of about 500mW / cm 2 The above achieves efficient utilization of platinum, thanks to the excellent electrode structure. The ordered carrier improves the material transfer capacity, while the composite carrier that couples electron and proton conduction improves the electrochemical reaction efficiency.

[0044] Example 3: Preparation of composite nanowire arrays of polyaniline and polythiophene for use as supercapacitor electrode materials

[0045] First, prepare a buffer solution with a NaCl concentration of 0.2 M, a KCl concentration of 3 mM, a sodium dihydrogen phosphate concentration of 2 mM, and a disodium hydrogen phosphate concentration of 8 mM; add aniline monomer, thiophene monomer, and surfactant to the above buffer solution, where the aniline monomer concentration is 0.1 M, the thiophene monomer concentration is 0.2 M, and the surfactant is sodium α-butene sulfonate and sodium hexadecylnaphthalene sulfonate at the same concentration. The total concentration of the surfactant in the electrolyte solution is 0.5 M. Continuously introduce argon gas into the above electrolyte solution at a gas flow rate of 10 mL / min for 50 min, and keep the electrolyte solution in a 50 °C constant temperature water bath for 60 min. Using a carbon fiber as the working electrode, first activate the working electrode with a scanning potential from 0 V to 0.5 V for 60 cycles. After the activation treatment, set the reaction potential to 0.95 V and the reaction time to 35 min to prepare a conductive polymer composite with an ordered nanowire array structure and use it as the electrode material of a supercapacitor. The cyclic voltammetry test curve is as Figure 7 shown. The cyclic voltammetry curve of this composite material has an approximately regular rectangular shape, making it a good electrode material for capacitors. At the same time, it also demonstrates its stability and good capacitance characteristics under fast charge and discharge conditions.

Claims

1. A method for preparing a conductive polymer composite material, comprising the following steps: 1), Prepare a buffer solution; 2), Add a conductive polymer monomer, a surfactant, and a monomer solution of a sulfonic acid group-containing organic polymer resin to the buffer solution in step 1), and after mixing, an electrolyte solution is obtained. The concentration of the sulfonic acid group-containing organic polymer resin monomer in the electrolyte solution is 0 - 0.2 M; 3), Pass an inert gas into the above electrolyte solution, and the gas passed in is nitrogen or argon; 4), Keep the electrolyte solution stored at a constant temperature; 5), After completing step 4), use a carbon carrier as the working electrode to form a three-electrode system in the electrolyte solution. First, activate it by cyclic voltammetry scanning; after the activation is completed, use the potentiostatic method to control the reaction potential and reaction time, and prepare a conductive polymer composite material with an ordered nanowire array structure on the surface of the carrier by electro-polymerization autocatalytic growth; the carbon carrier includes carbon paper, carbon cloth, and carbon fiber materials; the potential range of the activation treatment is 0 V to 0.5 V, and the number of scanning cycles is 60 - 100 cycles; in the potentiostatic method, set the reaction potential to 0.95 - 1.15 V, and the reaction time to 20 - 50 min; The composite material is an ordered composite nanowire array, and the components of the ordered composite nanowire array are one or a combination of two or more conductive polymers, or one or a combination of two or more conductive polymers and a sulfonic acid group-containing organic polymer resin; In the ordered composite nanowire array, the diameter of the nanowires is 10 - 60 nanometers, and the length of the nanowires is 2 - 10 micrometers; the arrangement of the nanowires is an ordered columnar arrangement or an ordered nanonetwork intertwined arrangement.

2. The preparation method according to claim 1, characterized in that: In step 1), the specific method for preparing the buffer solution is to take sodium chloride, potassium chloride, sodium dihydrogen phosphate, and disodium hydrogen phosphate with a certain concentration, and after mixing, a buffer solution is obtained. In the mixed buffer solution, the concentration of sodium chloride is 0.1 - 0.5 M, the concentration of potassium chloride is 1 - 5 mM, the concentration of sodium dihydrogen phosphate is 1 - 5 mM, and the concentration of disodium hydrogen phosphate is 5 - 10 mM.

3. The preparation method according to claim 1, characterized in that: In step 2), the conductive polymer monomer is one or more of aniline, pyrrole, and thiophene, and the total concentration of the conductive polymer monomer in the electrolyte solution is 0.1 - 0.5 M; the sulfonic acid group-containing organic polymer resin is one of perfluorosulfonic acid resin, non-perfluorosulfonic acid resin, or short-side-chain resin; the surfactant is one or two of sodium α-butene sulfonate, sodium hexadecylnaphthalene sulfonate, and sodium hexadecyl glycerol ether sulfonate, and the concentration of the surfactant in the electrolyte solution is 0.1 - 0.5 M.

4. The preparation method according to claim 1, characterized in that: In step 3), the flow rate of the gas passed in is 5 - 20 mL / min, and the continuous gas passing time is 45 - 90 min; in step 4), the constant-temperature storage is carried out in a constant-temperature water bath, the temperature in the constant-temperature water bath is 30 - 60 °C, and the heat preservation time is 30 - 60 min.

5. The preparation method according to claim 1, characterized in that: Regulate the diameter and length of the nanowires by changing reaction conditions such as reaction potential, reaction time, reaction temperature, and the concentration of the surfactant, and control the arrangement of the nanowires to be an ordered columnar arrangement or an ordered nanonetwork intertwined arrangement by regulating the diameter and length of the nanowires.

6. Use of an ordered array composite nanowire prepared by the preparation method according to any one of claims 1-5 in a supercapacitor, an ordered electrode carrier, and a solar cell.

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