阅读说明：本技术 一种有机无机复合热电薄膜及其制备方法 (Organic-inorganic composite thermoelectric film and preparation method thereof ) 是由 王黎明 覃小红 熊健 刘烨 俞建勇 于 2019-11-27 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薄膜及其制备方法，所述薄膜以双通氧化铝膜为模板，通过物理气相沉积，在衬底上制备无机热电纳米颗粒阵列；然后在其表面沉积导电聚合物薄膜，即得。本发明的方法简单，可控性高，有利于热电薄膜的大规模快速制备，并且无机热电纳米颗粒在聚合物基体中均匀分散，有利于获得高热电性能，具有很好的应用前景。(The invention relates to an organic-inorganic composite thermoelectric film and a preparation method thereof, wherein the film takes a double-pass alumina film as a template, and an inorganic thermoelectric nanoparticle array is prepared on a substrate through physical vapor deposition; and then depositing a conductive polymer film on the surface of the substrate to obtain the conductive polymer film. The method is simple, has high controllability, is beneficial to large-scale rapid preparation of the thermoelectric film, and the inorganic thermoelectric nano particles are uniformly dispersed in the polymer matrix, thereby being beneficial to obtaining high thermoelectric performance and having good application prospect.)

1. An organic-inorganic composite thermoelectric film comprising an array of inorganic thermoelectric nanoparticle materials uniformly distributed in a conductive polymer matrix.

2. The composite thermoelectric film as claimed in claim 1, wherein the conductive polymer is one or more of polyaniline, polypyrrole, polythiophene and its derivatives, and polyvinyltetrathiol based metal complexes; the inorganic thermoelectric nano-particle material is Bi₂Te₃、Sb₂Te₃、SnTe、CoSb₃And one or more of PbTe.

3. The composite thermoelectric film according to claim 1, wherein the content of the inorganic thermoelectric nanoparticles in the composite thermoelectric film is 1 to 90 wt%.

4. A preparation method of an organic-inorganic composite thermoelectric film comprises the following steps:

(1) attaching a double-pass alumina film on a substrate;

(2) depositing an inorganic thermoelectric material on the substrate obtained in the step (1) by a physical vapor deposition method, removing the bi-pass alumina film to obtain an inorganic thermoelectric nanoparticle array, then depositing a conductive polymer, and drying to obtain the organic-inorganic composite thermoelectric film.

5. The preparation method according to claim 4, wherein the thickness of the two-pass aluminum oxide film in the step (1) is less than 1 μm, and the diameter of the pores is less than 500 nm; the substrate is a silicon wafer, glass, a polyimide PI film or a polyethylene terephthalate PET film.

6. The preparation method according to claim 4, wherein the physical vapor deposition method in the step (2) is vacuum thermal evaporation, magnetron sputtering or ion plating; the method for depositing the conductive polymer comprises the following steps: drop coating, spin coating, chemical vapor deposition, or electrochemical deposition.

7. The method according to claim 4, wherein the inorganic thermoelectric material in the step (2) is Bi₂Te₃Base thermoelectric material, Sb₂Te₃Base thermoelectric material, SnTe base thermoelectric material, CoSb₃One or more of a base thermoelectric material and a PbTe base thermoelectric material; the conductive polymer is one or more of polyaniline, polypyrrole, polythiophene and derivatives thereof, and polyethylene tetrathiol based metal complex.

8. The method of claim 4, wherein the inorganic thermoelectric material deposited in step (2) has a thickness of less than 1 μm.

9. An organic-inorganic composite thermoelectric film prepared by the method of claim 4.

10. Use of the organic-inorganic composite thermoelectric film according to claim 1.

Technical Field

The invention belongs to the field of thermoelectric thin film materials and preparation thereof, and particularly relates to an organic-inorganic composite thermoelectric thin film and a preparation method thereof.

Background

The thermoelectric material is a functional material which directly converts thermal energy and electric energy into each other by utilizing the seebeck effect and the peltier effect of a semiconductor material. The thermoelectric conversion technology has the characteristics of small system volume, high reliability, no pollutant emission, wide applicable temperature range and the like, and is applied to the fields of recycling of industrial waste heat and automobile exhaust, micro power supply of aerospace detectors, micro-district cooling, biomedicine and the like. The characteristics of green and environmental protection can effectively relieve the increasingly serious problems of environmental pollution and energy crisis in the world at present, so that high-performance thermoelectric materials and high-efficiency thermoelectric power generation technologies are in wide attention internationally in recent years. The thermoelectric properties of a material are generally evaluated by a dimensionless thermoelectric figure of merit zT, which is σ S²T/kappa, sigma is the electrical conductivity, S is the seebeck coefficient, kappa is the thermal conductivity, T is the absolute temperature, sigma S²Is the power factor. The thermoelectric materials currently studied and used are mainly Bi applied near room temperature₂Te₃Base thermoelectric material CoSb for use in medium temperature region₃PbTe-based thermoelectric materials, SiGe-based thermoelectric materials used in high-temperature regions, and the like. Although these inorganic thermoelectric materials have good thermoelectric properties, their raw materials are expensive, the preparation process is complex and costly, it is difficult to prepare special-shaped and flexible devices, and they are toxic and bring about heavy metal pollution, which greatly limits their wide application.

Since the last 70 th century when conductive polymer materials with high electrical conductivity were reported, more and more researchers began to invest in the research of organic thermoelectric materials. The organic thermoelectric material has unique advantages, such as very low thermal conductivity, low raw material price, flexibility and easy large-scale preparation, and provides a new choice for room-temperature thermoelectric materials. However, the thermoelectric performance of organic thermoelectric materials is much lower than that of conventional inorganic thermoelectric materials. Recent research shows that the preparation of the organic-inorganic nano composite thermoelectric material is an effective way for improving the thermoelectric performance of the organic material, inorganic filling particles with high conductivity or high seebeck coefficient are compounded with a conductive polymer, and the conductivity or the seebeck coefficient of the polymer can be improved by utilizing the synergistic effect of the inorganic filling particles and the conductive polymer; in addition, the Seebeck coefficient of the material can be improved by the energy filtering effect at the interface of the two Materials, and the thermal conductivity is reduced by the phonon interface scattering effect generated by the nano-filler particles, so that the thermoelectric performance of the conductive polymer is effectively improved (ACSNano,2010,4, 2445-. However, nanoparticles tend to agglomerate, and the dispersion in organic thermoelectric materials is not controllable, which limits further improvement of thermoelectric performance (ACS applied materials & Interfaces,2010,2, 3170-. CN107964648A discloses a P-type Sb2Te3 composite CH3NH3I thermoelectric film and a preparation method thereof, but the method still cannot finely control the distribution of organic and inorganic thermoelectric materials in the composite film. Although the template is manufactured by etching the single-layer closely-packed polystyrene nanospheres, the organic-inorganic composite thermoelectric film (Nature Communications,2018,9,3817) with monodisperse nano-filler particles can be finally manufactured, but the method has complex process and poor controllability, and is not beneficial to large-scale production and preparation.

Disclosure of Invention

The invention provides an organic-inorganic composite thermoelectric film and a preparation method thereof, wherein inorganic thermoelectric nano-particles are monodisperse and uniformly distributed in an organic matrix, and the defects of complex process and poor controllability of the prior preparation technology are overcome; and then depositing a conductive polymer film on the surface of the film to obtain the organic-inorganic composite thermoelectric film.

The invention relates to an organic-inorganic composite thermoelectric film, which comprises inorganic thermoelectric nano-particle materials distributed in a conductive polymer matrix.

The conductive polymer is one or more of polyaniline, polypyrrole, polythiophene and derivatives thereof, and polyethylene tetrathiol-based metal complex; the inorganic thermoelectric nano-particle material is Bi₂Te₃、Sb₂Te₃、SnTe、CoSb₃And one or more of PbTe. The content of the inorganic thermoelectric nano particles in the composite thermoelectric film is 1-90 wt%.

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

(1) attaching a double-pass alumina film on a substrate;

(2) and (2) depositing the inorganic thermoelectric material on the substrate obtained in the step (1) by using an inorganic thermoelectric material as a target material through a physical vapor deposition method, removing the bi-pass alumina film by using an adhesive tape to obtain an inorganic thermoelectric nanoparticle array, then depositing a conductive polymer, and drying to obtain the organic-inorganic composite thermoelectric film.

The preferred mode of the above preparation method is as follows:

the thickness of the double-pass aluminum oxide film in the step (1) is less than 1 μm, and the diameter of the hole is less than 500 nm; the substrate is a silicon wafer, glass, a polyimide PI film or a polyethylene terephthalate PET film.

The physical vapor deposition method in the step (2) is vacuum thermal evaporation, magnetron sputtering or ion plating; the method for depositing the conductive polymer comprises the following steps: drop coating, spin coating, chemical vapor deposition, or electrochemical deposition.

The inorganic thermoelectric material in the step (2) is Bi₂Te₃Base thermoelectric material, Sb₂Te₃Base thermoelectric material, SnTe base thermoelectric material, CoSb₃One or more of a base thermoelectric material and a PbTe base thermoelectric material; the conductive polymer is one or more of polyaniline, polypyrrole, polythiophene and derivatives thereof, and polyethylene tetrathiol based metal complex.

The thickness of the inorganic thermoelectric material deposited in the step (2) is less than 1 μm.

The drying in the step (2) is carried out for 6-24 hours under the vacuum condition of 60 ℃.

The invention provides an organic-inorganic composite thermoelectric film prepared by the method.

The invention provides an application of the organic-inorganic composite thermoelectric film.

Advantageous effects

The method has the advantages of simple process, low cost, short period and high controllability, and is suitable for large-scale industrial production; the method is also suitable for preparing the organic-inorganic composite thermoelectric film on the flexible substrate, and the composite film has good flexibility and can be bent and applied to the field of wearable electronic devices.

Drawings

FIG. 1 shows the PEDOT: PSS-Bi from example 1₂Te₃A digital photographic image of the composite thermoelectric film;

FIG. 2 shows the PEDOT: PSS-Bi from example 1₂Te₃Scanning electron microscope images of the composite thermoelectric thin film;

FIG. 3 shows the PEDOT: PSS-Bi from example 1₂Te₃Electrical conductivity of the composite thermoelectric film;

FIG. 4 shows the PEDOT: PSS-Bi from example 1₂Te₃The seebeck coefficient of the composite thermoelectric film;

FIG. 5 shows the PEDOT: PSS-Bi from example 1₂Te₃Power factor of the composite thermoelectric film.

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. Bi used in the examples of the present invention₂Te₃Powder and Sb₂Te₃The powder is prepared from Sichuan high-purity material technology, and is polyethylene dioxythiophene-polystyrene sulfonate (PEDOT: PSS) aqueous solution (type Orgacon)^TMICP 1050) and Polyaniline (PANI) powders were produced by Sigma-Aldrich, and bi-pass AAO films were produced by shenzhen topology essence film science and technology ltd.