阅读说明：本技术 一种高电导率pedot:pss自支撑厚膜、制备方法及其应用 (High-conductivity PEDOT (Poly ethylene glycol Ether-styrene) PSS (Poly ethylene styrene) self-supporting thick film, preparation method and application thereof ) 是由 姚洪岩 孙忠晖 关绍巍 于 2019-10-22 设计创作，主要内容包括：一种高电导率PEDOT:PSS自支撑厚膜、制备方法及其应用,属于导电高分子材料领域。本发明中高电导率PEDOT:PSS自支撑厚膜的制备方法,其步骤如下,首先将有机掺杂剂加入到PEDOT:PSS水溶液中,搅拌下配成均匀混合溶液；然后该混合溶液滴涂至清洗后的玻璃片上,烘干成膜；再将得到的膜冷却后放在水中浸泡并搅拌；最后将膜从水中取出后,烘干即得到高电导率PEDOT:PSS自支撑厚膜,膜的厚度范围为2～20μm。本发明制备的厚膜的电导率比本征PEDOT:PSS膜提高了1000多倍。这种自支撑PEDOT:PSS厚膜不需要基底,制备方法简单、成本低,厚度具有优良的可调控性,并且具有优异的柔韧性,在柔性电子、热电材料等领域具有巨大的发展潜力和应用价值。(A high-conductivity PEDOT PSS self-supporting thick film, a preparation method and application thereof belong to the field of conductive high polymer materials. The preparation method of the high-conductivity PEDOT and PSS self-supporting thick film comprises the following steps of firstly adding an organic dopant into a PEDOT and PSS aqueous solution, and preparing a uniform mixed solution under stirring; then the mixed solution is dripped on a cleaned glass sheet and dried to form a film; cooling the obtained film, soaking in water and stirring; and finally, taking the film out of water, and drying to obtain the high-conductivity PEDOT (PSS) self-supporting thick film, wherein the thickness range of the film is 2-20 mu m. The conductivity of the thick film prepared by the method is improved by more than 1000 times than that of an intrinsic PEDOT/PSS film. The self-supporting PEDOT/PSS thick film does not need a substrate, has simple preparation method, low cost, excellent controllability of thickness and excellent flexibility, and has huge development potential and application value in the fields of flexible electronics, thermoelectric materials and the like.)

1. A preparation method of a high-conductivity PEDOT/PSS self-supporting thick film comprises the following steps:

1) adding an organic doping agent into a PEDOT (PSS) aqueous solution, and preparing a uniform mixed solution under stirring;

2) dripping the mixed solution obtained in the step 1) on a cleaned glass sheet, and drying to form a film;

3) cooling the film obtained in the step 2), and then soaking in water and stirring;

4) and taking the film out of the water, and drying to obtain the high-conductivity PEDOT (PSS) self-supporting thick film, wherein the thickness range of the film is 2-20 mu m.

2. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: in the step 1), the organic dopant is one or more of ethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, N-dimethylformamide, sorbitol, dimethyl sulfoxide, N-methylpyrrolidone or glycerol.

3. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: in the step 1), the volume fraction of the organic dopant in the PEDOT/PSS aqueous solution is 1-50%.

4. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: the stirring time in the step 1) is 1-20 h, and the stirring speed is 100-1000 rmp.

5. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: in the step 2), the drying temperature is 30-200 ℃, and the drying time is 1-20 h.

6. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: in the step 3), soaking the PEDOT, namely the PSS thick film in water and stirring for 1-20 h; the stirring speed is 100 to 1000 rmp.

7. PSS self-supporting thick film of high conductivity PEDOT as defined in claim 1, characterized in that: in the step 4), the drying temperature is 30-200 ℃, and the drying time is 0.5-20 h.

8. A self-supporting thick film of high conductivity PEDOT PSS, characterized by: is prepared by the method of any one of claims 1 to 7.

9. PST thick self-supporting film according to claim 8, for use in the field of flexible electronic or thermoelectric materials.

Technical Field

The invention belongs to the field of conductive high polymer materials, and particularly relates to a high-conductivity PEDOT (Poly ethylene glycol Ether-Co-Polymer) PSS (Poly ethylene-propylene-Ether-Co-Polymer) self-supporting thick film, a preparation method and application thereof.

Background

The conductive polymer material is a novel functional material, has the unique advantages of good stability, low toxicity, easy processing and the like, and has great application potential in the fields of thermoelectric materials, electrode materials, sensors, metal corrosion prevention, capacitors and the like.

Poly 3, 4-ethylenedioxythiophene p-styrenesulfonic acid (PEDOT: PSS) is one of the most popular conductive polymer materials at present, and a PEDOT: PSS film can be prepared by a solution processing method, so that the poly 3, 4-ethylenedioxythiophene p-styrenesulfonic acid film has a remarkable advantage in practical application. Very low conductivity of intrinsic PEDOT PSS films prepared directly from PEDOT PSS solutions (<1S cm^-1) However, many application fields have high requirements on the conductivity of the PEDOT/PSS film, so that the improvement of the conductivity of the PEDOT/PSS film is particularly important.

For thermoelectric materials, high electrical conductivity is crucial to realizing high power factor and high thermoelectric performance; for electrode materials, high conductivity can significantly increase capacitance and energy density; in the capacitor, high conductivity is advantageous for improving charge and discharge properties and electrostatic properties.

Several methods for increasing the conductivity of PEDOT: PSS films have been reported in the literature, such as acid (sulfuric acid, formic acid, etc.) treatment and organic solvent (dimethylsulfoxide, tetrahydrofuran, etc.) doping. However, these methods are not ideal for conductivity enhancement of thick PEDOT: PSS films (greater than 1 micron). Currently available PEDOT: PSS films are generally prepared by spin coating onto a substrate material. Compared with the self-supporting thick film, the self-supporting thick film does not need a substrate, has simple preparation method, low cost, excellent controllability of thickness and excellent flexibility, and has huge development potential and application value in the fields of flexible electronics, thermoelectric materials and the like.

Disclosure of Invention

The invention aims to provide a high-conductivity PEDOT/PSS self-supporting thick film, a preparation method and application thereof aiming at the defects of the prior art.

The preparation method of the high-conductivity PEDOT/PSS self-supporting thick film comprises the following steps:

1) adding an organic doping agent into a PEDOT (PSS) aqueous solution, and preparing a uniform mixed solution under stirring;

2) dripping the mixed solution obtained in the step 1) on a cleaned glass sheet, and drying to form a film;

3) cooling the film obtained in the step 2), and then soaking in water and stirring;

4) and taking the film out of the water, and drying to obtain the high-conductivity PEDOT/PSS self-supporting thick film (the film can exist independently from the glass sheet), wherein the thickness range of the film is 2-20 μm.

Preferably, in step 1), the organic dopant used is one or more of ethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, polyethylene glycol 1000, N-dimethylformamide, sorbitol, dimethyl sulfoxide, N-methylpyrrolidone, and glycerol;

preferably, in the step 1), the volume fraction of the organic dopant in the PEDOT/PSS aqueous solution is 1-50%, the stirring time is 1-20 h, and the stirring speed is 100-1000 rmp;

preferably, in the step 2), the drying temperature is 30-200 ℃, and the drying time is 1-20 h;

preferably, in the step 3), the PEDOT and PSS thick film is soaked in water and stirred for 1-20 h; the stirring speed is 100-1000 rmp;

preferably, in the step 4), the drying temperature is 30-200 ℃ and the drying time is 0.5-20 h.

Compared with the prior art, the invention has the beneficial effects that:

the invention adopts the methods of doping organic dopant and soaking in solvent to improve the PEDOT-PSS thick filmThe conductivity of (a) is improved by more than 1000 times compared with the intrinsic PEDOT to PSS film. The PEDOT/PSS self-supporting thick film with better conductivity and power factor is obtained by optimizing the type and volume fraction of the doped organic dopant, and the conductivity can reach 1416S cm^-1. Compared with the film prepared by the prior spin coating method, the self-supporting PEDOT/PSS thick film does not need a substrate, has simple preparation method, low cost, excellent controllability of thickness and excellent flexibility, and can be used for flexible electronic and thermoelectric materials (the power factor can reach 61 mu W m at most)^-1K^-2) And the like, and has great development potential and application value.

Drawings

FIG. 1 is a plot of conductivity of PEDOT: PSS thick films as a function of volume fraction of doped polyethylene glycol 200.

FIG. 2 is a digital photograph of flat (a) and curved (b) of a self-supporting thick film of high conductivity PEDOT prepared in example 2 PSS. It can be observed that the PEDOT: PSS thick film is very flat and can be bent at will, is very flexible and exhibits good self-supporting properties.

FIG. 3 is an atomic force microscope image of a high conductivity PEDOT: PSS film prepared in example 2. In the case of the height diagram of a and the phase diagram of b, it can be observed that more fibrous-connected PEDOT chains are present, leading to a significant increase in conductivity.

FIG. 4 is a Raman spectrum of the freestanding thick film of high conductivity PEDOT: PSS prepared in example 2. 1436cm can be observed^-1The shift in raman peak indicates: PEDOT is changed from a benzene type conformation to a quinoid conformation, and the change of the conformation leads the conductivity and the Seebeck coefficient to be obviously improved, so that the improvement of the power factor is more obvious.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments that can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step are within the scope of the present invention.

The aqueous PEDOT: PSS solutions of the following examples were purchased from Heraeus, having a solids content of 1.3% wt and a weight ratio of PEDOT to PSS of 1: 2.5.