阅读说明：本技术 一种有机/无机复合热电纤维及其制备和应用 (Organic/inorganic composite thermoelectric fiber and preparation and application thereof ) 是由 李耀刚 徐海丰 侯成义 王宏志 张青红 于 2020-03-13 设计创作，主要内容包括：本发明涉及一种有机/无机复合热电纤维及其制备和应用,所述热电纤维的有机组分为聚(3,4-乙烯二氧噻吩)-聚(苯乙烯磺酸酯)PEDOT:PSS,无机组分为碲纳米线Te NWs,Te NWs取向分布于PEDOT:PSS纤维中,采用湿法纺丝制备而成。本发明制备的复合纤维具有良好的热电性能,在柔性热电可穿戴领域具有广阔的应用前景。本发明制备工艺简单、具备连续化生产的潜力。(The invention relates to an organic/inorganic composite thermoelectric fiber, and preparation and application thereof, wherein the organic component of the thermoelectric fiber is poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonate) PEDOT: PSS, the inorganic component is tellurium nanowires Te NWs, and the Te NWs are oriented and distributed in the PEDOT: PSS fiber and prepared by wet spinning. The composite fiber prepared by the invention has good thermoelectric performance and wide application prospect in the field of flexible thermoelectric wearability. The preparation method is simple in preparation process and has the potential of continuous production.)

1. An organic/inorganic composite thermoelectric fiber is characterized in that the fiber comprises a composite fiber of poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonate) PEDOT, PSS and tellurium nanowires Te NWs.

2. The thermoelectric fiber according to claim 1, wherein the mass ratio of PEDOT to PSS to Te NWs is 1:0.1 to 1: 1.

3. The thermoelectric fiber of claim 1, wherein the Te NWs is oriented in the composite fiber.

4. The thermoelectric fiber according to claim 1, wherein the thermoelectric fiber is obtained by wet spinning of PEDOT PSS, Te NWs, polyethylene glycol PEG.

5. A preparation method of an organic/inorganic composite thermoelectric fiber comprises the following steps:

(1) adding tellurium nanowires Te NWs, PEDOT, PSS conductive particles and polyethylene glycol into deionized water, mixing, stirring and ultrasonically treating to obtain a spinning solution, and then carrying out wet spinning to obtain fibers;

(2) and (3) sealing the fibers obtained in the step (2) in a hydrothermal kettle filled with glycol, heating, and cooling to obtain the organic/inorganic composite thermoelectric fibers.

6. The preparation method according to claim 5, wherein the tellurium nanowires Te NWs in the step (1) are specifically as follows: adding tellurium oxide, polyvinylpyrrolidone and potassium hydroxide into an ethylene glycol solvent, carrying out hydrothermal reaction, cooling and washing to obtain the TenWs.

7. The method according to claim 5, wherein the concentration of PEDOT/PSS in the dope of step (1) is 18 to 25 mg-m L^-1(ii) a The mass ratio of PEDOT to PSS to Te NWs to polyethylene glycol is 1:0.1: 0.1-1: 1: 5.

8. The preparation method according to claim 5, wherein the wet spinning in the step (1) comprises the steps of filling the spinning solution into an injector, uniformly extruding the spinning solution into a coagulating bath by using a syringe pump, standing the spinning solution in the coagulating bath for 10 to 30min, wherein the specification of a needle used by the injector is 12 to 18G, and the extrusion speed of the syringe pump is 1 to 15m L-h^-1The coagulation bath was isopropanol.

9. The preparation method according to claim 5, wherein the heating treatment temperature in the step (2) is 150 ℃ to 170 ℃ and the treatment time is 0.5h to 3 h.

10. Use of the organic/inorganic composite thermoelectric fiber according to claim 1.

Technical Field

The invention belongs to the field of flexible thermoelectric materials and preparation and application thereof, and particularly relates to an organic/inorganic composite thermoelectric fiber and preparation and application thereof.

Background

With the miniaturization of chips, the improvement of adaptability of circuits and hardware and the popularization of mobile networks, a large number of wearable electronic devices and sensors are emerged in the market in recent years, but most of wearable devices are still powered by batteries, and the batteries need to be charged and replaced frequently, while some wearable electronic devices need to be operated autonomously and uninterruptedly, for example, wearable medical sensors used for monitoring physical sign states of patients, and the popularization and application of the wearable medical sensors are limited due to the manual replacement of the batteries and the charging.

Since flexible thermoelectric materials are receiving more and more attention because they can directly convert thermal energy into electric energy and realize continuous self-power supply of wearable electronic devices through the temperature gradient between human skin and the surrounding environment, how to prepare high-performance flexible thermoelectric materials and effectively combine the materials with fabrics is a crucial issue.

Conductive polymer materials are an important branch of flexible thermoelectric materials, and are receiving attention due to their light weight and flexibility. Moreover, the novel commercialized conducting polymer products have low cost, good environmental stability and no toxicity, and are a better choice for constructing flexible thermoelectric materials. The PEDOT and PSS are flexible thermoelectric materials with excellent performance, have good film forming property, can effectively improve the conductivity of the materials after post-treatment, but have limited application in the thermoelectric field due to low Seebeck coefficient. Therefore, researchers have used inorganic thermoelectric materials with high Seebeck coefficients to improve the thermoelectric properties of PEDOT: PSS, and researchers (Energy,2017,125:519-525) have used inorganic thermoelectric materials to improve the thermoelectric properties of PEDOT: PSSThe SS composite tellurium nano-rod is used for improving the Seebeck coefficient of a PEDOT-PSS composite film from 10 to 50 muV.K^-1。

At present, the thermoelectric performance of a composite film based on PEDOT: PSS is effectively improved by an organic-inorganic composite method, but the film thermoelectric material has certain problems in wearable application: firstly, the thin-film device usually occupies a large area, which seriously affects the aesthetic feeling of the fabric; second, film devices are often dense, which affects the breathability and comfort of the fabric. In order to solve the problem, the PEDOT/PSS/Te NWs organic/inorganic composite thermoelectric fiber is constructed by a wet spinning technology, compared with a thermoelectric film, the fiber can be directly sewn into a fabric, the appearance and the air permeability of the fabric are not influenced, and the bonding property of a thermoelectric material and the fabric is improved.

Disclosure of Invention

The invention aims to solve the technical problem of providing an organic/inorganic composite thermoelectric fiber, and preparation and application thereof, and overcoming the problem of poor bonding property between a thin film thermoelectric material and a fabric in the prior art. The invention is prepared by PEDOT, PSS, Te NWs and polyethylene glycol (PEG) through wet spinning.

The invention provides an organic/inorganic composite thermoelectric fiber, which comprises a composite fiber of organic component poly (3, 4-ethylenedioxythiophene) -poly (styrene sulfonate) PEDOT, PSS and inorganic component tellurium nanowire Te NWs.

The mass ratio of PEDOT to PSS to Te NWs is 1: 0.1-1: 1.

The Te NWs is oriented and distributed in the composite fiber.

The thermoelectric fiber is obtained by carrying out wet spinning on PEDOT (PSS), Te NWs and polyethylene glycol (PEG)

The invention relates to a preparation method of an organic/inorganic composite thermoelectric fiber, which comprises the following steps:

(1) adding tellurium nanowires Te NWs, PEDOT, PSS conductive particles and polyethylene glycol into deionized water, mixing, stirring and ultrasonically treating to obtain a homogeneous spinning solution, and then carrying out wet spinning to obtain fibers;

(2) and (3) sealing the fibers obtained in the step (2) in a hydrothermal kettle filled with glycol, placing the hydrothermal kettle in an oven for heating treatment, and cooling to obtain the organic/inorganic composite thermoelectric fibers.

The tellurium nanowires Te NWs in the step (1) are specifically as follows: adding tellurium oxide, polyvinylpyrrolidone and potassium hydroxide into an ethylene glycol solvent, carrying out hydrothermal reaction, cooling and washing to obtain Te NWs.

The mass ratio of the tellurium oxide to the polyvinylpyrrolidone to the potassium hydroxide is 1:1: 0.59-1: 3: 1.77; the hydrothermal reaction time is 12-24 h, and the hydrothermal temperature is 140-180 ℃.

The molecular weight of the polyvinylpyrrolidone is 40000.

The concentration of PEDOT to PSS in the spinning solution in the step (1) is 18-25 mg.m L^-1(ii) a The mass ratio of PEDOT to PSS to Te NWs to polyethylene glycol is 1:0.1: 0.1-1: 1:5

Further, the preferable value of the mass ratio of PEDOT to PSS to Te NWs to polyethylene glycol is 1:1: 5;

the molecular weight of the polyethylene glycol is 400.

The stirring time in the step (1) is 0.5-2 h, and the ultrasonic time is 0.5-2 h.

The wet spinning in the step (1) is specifically that a spinning solution is filled into an injector, the spinning solution is extruded into a coagulating bath at a constant speed by using an injection pump, the spinning solution is kept stand for 10-30 min in the coagulating bath, the specification of a needle head used by the injector is 12-18G, and the extrusion speed of the injection pump is 1-15 m L & h^-1The coagulation bath was isopropanol.

And (3) sealing the fibers in the step (2) in a hydrothermal kettle filled with glycol, wherein the mass ratio of the fibers to the glycol is 1: 10-1: 20.

The heating treatment temperature in the step (2) is 150-170 ℃, and the treatment time is 0.5-3 h.

The invention provides an organic/inorganic composite thermoelectric fiber prepared by the method.

The invention provides an application of the organic/inorganic composite thermoelectric fiber, such as the field of thermoelectric wearability.

Advantageous effects

(1) The preparation method is simple and feasible, and has the potential of continuous production;

(2) the organic/inorganic composite thermoelectric fiber has good thermoelectric performance;

(3) the organic/inorganic composite thermoelectric fiber can be directly woven into fabrics, and has good application prospect in the field of thermoelectric wearability.

Drawings

FIG. 1 is a schematic diagram of a self-contained test system;

FIG. 2 is a schematic diagram of a wet spinning process (a) and a digital photograph (b) of the fiber prepared in example 2;

FIG. 3 is a digital photograph of fibers prepared in example 2 woven directly into a fabric;

fig. 4 is an SEM photograph of the composite fiber prepared in example 3, in which (a) is an SEM photograph of a cross section and (b) is an SEM photograph of a surface.

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.