KR101792206B1 - Freestanding flexible thermoelectric composite structure, thermoelectric device including the same, and method for preparing the freestanding flexible thermoelectric composite structure - Google Patents

Abstract

A polymer film having a glass transition temperature (Tg) of 50 ° C or higher, and a thin film coated on one side of the polymer film with a material having a Seebeck coefficient of ± 1 kN / K or higher, can improve thermoelectric properties , The thermoelectric element including the thermoelectric composite structure can be mounted on a device having various structures.

Description

      BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-sustaining flexible thermoelectric composite structure, a thermoelectric device including the same, and a manufacturing method of the self-

The present invention relates to a flexible thermoelectric composite structure, a thermoelectric device including the same, and a method of manufacturing the flexible thermoelectric composite structure.

In the thermoelectric field, research on high-efficiency thermoelectric materials is very important. The properties of the thermoelectric material are expressed in terms of the so-called dimensionless merit (ZT) value:

   [Equation 1]

Where S is the Seebeck coefficient, sigma is the electrical conductivity, k is the thermal conductivity, and T is the absolute temperature.

In order to obtain a high performance index, the Seebeck coefficient and electrical conductivity should be large, and the thermal conductivity should be small. Thermal conductivity is related to the electrical conductivity of the material. The thermal conductivity is related to the thermal conductivity by the electron transfer by the Biedemann-Franz law and the thermal conductivity by the phonon through the material lattice.

Accordingly, various studies have been made to control the selection of materials and the structure of the materials.

Generally, the thermoelectric material used in a thermoelectric device is an inorganic material. However, the thermoelectric element including the thermoelectric material using the inorganic material has a high density, a heavy weight, and is not flexible, so that the applicability to various devices is very low.

Accordingly, there is still a need for a thermoelectric material having a novel structure which can be mounted on an apparatus having various structures and thermoelectric properties are improved.

One aspect is to provide a flexible thermoelectric composite structure having improved thermoelectric properties.

Another aspect of the present invention is to provide a thermoelectric device including the thermoelectric composite structure mountable on an apparatus having various structures.

Another aspect provides a method of manufacturing the flexible thermoelectric composite structure.

According to one aspect,

A polymer membrane having a glass transition temperature (Tg) of 50 DEG C or higher; And

And a thin film coated on one side of the polymer membrane and coated with a material having a Seebeck coefficient of ± 1 kN / K or more.

According to another aspect,

There is provided a thermoelectric element including the above-described flexible thermoelectric composite structure.

According to another aspect,

Coating a thin film of a material having a Seebeck coefficient of 1 1 / K or more on one side of the substrate;

Applying a polymer precursor solution for forming a polymer having a glass transition temperature (Tg) of 50 DEG C or higher on the upper surface of the thin film;

Forming a polymer film on the upper surface of the material thin film by curing the polymer precursor polymer precursor solution; And

And separating the polymer film formed on the upper surface of the material thin film from the substrate to produce the flexible thermoelectric composite material structure.

The flexible thermoelectric hybrid structure according to one aspect includes a polymer membrane having a glass transition temperature (Tg) of 50 ° C or higher and a thin film coated with a substance having a Seebeck coefficient of ± 1 kN / K or more on one side of the polymer membrane, And the thermal conductivity can be reduced to improve the thermoelectric properties. The flexible thermoelectric composite structure may be a stand-alone flexible thermoelectric hybrid structure, and the thermoelectric device including the same may be mounted on a device having various structures.

1 is a schematic diagram showing carrier behavior in a thermoelectric device including a flexible thermoelectric hybrid structure according to an embodiment.
2 is a schematic view showing a flexible thermoelectric hybrid structure according to one embodiment.
3 is a flowchart illustrating a method of manufacturing a flexible thermoelectric hybrid structure according to an embodiment of the present invention.
Figs. 4 and 5 are images obtained by scanning electron microscopy (SEM) of the cross section of the thermoelectric composite structure manufactured in Example 1 and Comparative Example 1, respectively.
6 is a graph showing the electrical conductivities of the thermoelectric composite structures manufactured in Example 1 and Comparative Example 1, respectively.
7 is a graph showing the seeback coefficient of the thermoelectric composite structure manufactured by Example 1 and Comparative Example 1, respectively.
FIG. 8 is a graph showing power factors of the thermoelectric composite structures manufactured according to Example 1 and Comparative Example 1, respectively.

Hereinafter, a flexible thermoelectric composite structure, a thermoelectric element including the same, and a method of manufacturing the flexible thermoelectric composite structure according to an exemplary embodiment will be described in detail with reference to the accompanying drawings. The following is presented as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims. In the present specification and drawings, constituent elements having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

The flexible thermoelectric composite structure according to one embodiment may include a polymer membrane having a glass transition temperature (Tg) of 50 ° C or higher and a thin film coated with a material having a Seebeck coefficient of ± 1 kN / K or higher on one surface of the polymer membrane. Preferably, the polymer film may have a glass transition temperature (Tg) of 200 DEG C or higher. The material may be localized in a direction away from a portion where the coated thin film and the polymer membrane are in contact with each other.

The thermoelectric properties of the flexible thermoelectric composite structure can be improved, and the weight can be reduced.

The thin film may be n-type or p-type.

The material may be selected from organic, inorganic, or organic complexes.

The organic / inorganic hybrid material may include a blend of the organic material and the inorganic material, a composite on which the inorganic material is coated on the surface of the organic material, or a composite on which the organic material is coated on the inorganic material surface.

1 is a schematic diagram showing carrier behavior in a thermoelectric device including a flexible thermoelectric hybrid structure according to an embodiment.

Referring to FIG. 1, a thermoelectric device including a flexible thermoelectric hybrid structure according to an embodiment exhibits thermoelectric characteristics by movement of carriers indicating charge when a temperature gradient occurs at both ends of the thermoelectric device. At this time, the flexible thermoelectric hybrid structure according to one embodiment can control the type of carriers representing the charge contained therein to n-type (free electrons) or p-type (free holes).

Generally, since the polymer film is an insulating material, it may interfere with the carrier movement path. As a result, the thermoelectric element including the thermoelectric composite structure composed of the polymer membrane / thermoelectric material thin film can be reduced in electric conductivity and deteriorated in thermoelectric properties.

To solve this problem, a method of increasing the content of a thermoelectric material exhibiting thermoelectric properties has been used in a thermoelectric composite structure composed of a conventional polymer membrane / thermoelectric material thin film.

However, in this case, due to the high density of the inorganic materials in the thermoelectric material, the weight of the thermoelectric composite structure composed of the polymer membrane and the inorganic thin film is increased, making it impossible to be applied to devices having various structures.

Also, in the case where the thermoelectric material has a low dispersibility property in the polymer solution, the thermoelectric material may cause coagulation phenomenon. As a result, the electrical conductivity due to the obstruction of the movement of the carrier is lowered, and the thermoelectric property may be deteriorated. As a result, there are limitations on the materials that can be used as thermoelectric materials.

Further, when a thermoelectric material is directly applied onto a polymer substrate, there is a limitation in selecting a solvent for dispersing the thermoelectric material depending on the properties of the substrate. In other words, when a thermoelectric material is dispersed in a solvent having no affinity for a substrate, a uniform thin film can not be formed, and the thermoelectric properties may be deteriorated.

The flexible thermoelectric composite structure according to an embodiment can secure electrical conductivity of the thermoelectric composite structure because the material is localized on the surface of the thin film. Also, the thermoelectric composite structure may include a polymer membrane having a glass transition temperature (Tg) of preferably 200 ° C or higher, and may be applied to an apparatus such as an automobile in which heat of 200 ° C or more is generated.

The flexible thermoelectric composite structure according to one embodiment is a method of fabricating a structure by applying a polymer solution to the top of a thermoelectric material. Therefore, there is no restriction on the use of a solvent for a thermoelectric material existing in a method of applying a material on a flexible substrate.

The organic material or the inorganic material may be a one-dimensional nanomaterial.

As used herein, "one-dimensional nanomaterial" refers to a nano-sized material having nanoscale diameters and aspect ratios of greater than 1, which are in point contact with adjacent elements. The one-dimensional nanomaterial has a diameter of 1 nm to 100 nm, and includes both "single" and "plural" nanomaterials.

The one-dimensional nanomaterial can restrict the movement of the phonon moving to a relatively short wavelength as compared with the electron movement due to the increased interface by securing the path through which the carrier moves. Accordingly, the flexible thermoelectric composite structure including the inorganic material may exhibit an effect of reducing thermal conductivity.

The organic material is selected from a single layer wall or a multilayer wall carbon nanotube, a graphene, a polyacetylene polymer, a polypyrrole polymer, a polythiophene polymer, a polyaniline polymer, a polyphenylene sulfide polymer, and a polyphenylene oxide polymer It may be more than one kind. The graphene may have a thickness of about 1 nm to 10 nm. The organic material may further include a polymer exhibiting conductivity of about 1 (S / cm) to 10,000 (S / cm) in addition to the above-described polymer.

The inorganic material may be at least one selected from a nanoparticle consisting of a transition metal, a rare earth element, at least one element selected from the group 13 elements, the group 14 elements, and the group 16 elements, a nanowire, a nanobelt, a nano ribbon, have.

The inorganic material may be selected from the group consisting of, for example, tellurium nanoparticles, tellurium nanowires, tellurium nanobelts, tellurium nanoribbons, bismuth nanoparticles, bismuth nanowires, bismuth nanobelts, bismuth nanoribbons, selenium nanoparticles, selenium nanowires , A selenium nano belt, a selenium nano ribbon, an antimony nanoparticle, an antimony nanowire, an antimony nanobelt, an antimony nanoribbon, and a combination thereof.

As used herein, the term "nanowire" refers to a line having a diameter of nano-level, and is not limited in length and exhibits an aspect ratio of about 100 or more. As used herein, "nanobelts" refers to belts having nano-level thicknesses and widths. As used herein, "nanoribbons" are ribbons having a nano-level width, which means that the aspect ratio is about 10 or more.

The inorganic material may include, for example, tellurium nanoparticles, bismuth nanoparticles, or Bi ₂ Te ₃ nanoparticles.

The content of the material may be 0.01 to 90 parts by weight, for example, 0.01 to 70 parts by weight, for example, 1 to 50 parts by weight, and may be, for example, 1 to 30 parts by weight based on 100 parts by weight of the thermo- Weight portion. Even within this content range, it is possible to secure a sufficient electric conductivity of the thermoelectric composite structure including the above material.

The polymer film may include at least one polymer selected from the group consisting of polyimide, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polyvinylidene, polyvinylidene fluoride, polystyrene, and urethane- have.

The polymer membrane may include, for example, a polymer including a repeating unit represented by the following formula (1)

≪ Formula 1 >

           In Formula 1,

           Y may be a divalent organic group,

     n may be an integer of 1,000 to 1,500,000.

    The Y in the formula (1) may include, for example, at least one selected from the organic groups represented by the following formulas (1-1) to (1-14)

&Lt; Formula 1-1 > < EMI ID =

&Lt; Chemical Formula 1-3 >

&Lt; Formula 1-5 > < Formula 1-6 >

&Lt; Formula 1-7 > < Formula 1-8 >

&Lt; Formula 1-9 > < Formula 1-10 >

&Lt; Formula 1-11 > < Formula 1-12 &

&Lt; Formula 1-13 > < Formula 1-14 &

   The Y in the above formula (1) may be, for example, a divalent organic group derived from diamine benzoic acid.

    The n in Formula 1 may be an integer of 10,000 to 500,000, for example.

   The polymer membrane can be used in a device that generates high heat including a polymer as described above, and can have a flexible property. Therefore, the flexible thermoelectric hybrid structure can be mounted on an apparatus having various structures such as a curved surface.

   The thermoelectric element according to another embodiment may include the above-described flexible thermoelectric hybrid structure. The above-mentioned flexible thermoelectric composite structural member can be usefully used as a thermoelectric material. The thermoelectric element may be a p-type or n-type thermoelectric element. Such a thermoelectric element means that the flexible thermoelectric material is formed into a predetermined shape, for example, a rectangular parallelepiped shape.

   The thermoelectric module may employ a thermoelectric module in which p-type and n-type thermoelectric materials are alternately arranged. The form of the thermoelectric module is not particularly limited, but may be, for example, a film form including p-type and n-type thermoelectric materials.

   The thermoelectric element may be combined with an electrode to exhibit a cooling effect by application of a current, or may be a component capable of exhibiting a power generation effect due to a temperature or a temperature difference.

    According to another embodiment of the present invention, there is provided a method of fabricating a flexible thermoelectric composite structure, including: coating a thin film of a material having a Seebeck coefficient of ± 1 kN / K or more on one surface of the substrate; Applying a polymer precursor solution for forming a polymer having a glass transition temperature (Tg) of 50 DEG C or higher on the upper surface of the thin film; Forming a polymer film on the upper surface of the material thin film by curing the polymer precursor polymer precursor solution; And separating the polymer film formed on the upper surface of the thin film material from the substrate to produce the above-described flexible thermoelectric composite material structure.

    First, a substrate is prepared. The substrate may include glass, ceramic, stainless steel, metal, and / or polymer substrates.

    Next, a material having a Seebeck coefficient of ± 1 kN / K or more, for example, an organic material, an inorganic material, or an organic-inorganic composite thin film is coated on one surface of the substrate (S1 step). As the organic material, inorganic material, or organic-inorganic hybrid material, the same materials as those described above may be used.

    The step of coating the material thin film may include a spin coating method, a doctor blade method, a vacuum filtration method, or a sedimentation method. Of these, the spin coating method is capable of coating a thin film of uniform thickness with a small amount of inorganic material. The thickness of the material thin film may be, for example, 10 nm to 50 탆.

    Next, a polymer precursor solution for forming a polymer having a glass transition temperature (Tg) of 50 ° C or higher is applied to the upper surface of the thin film of material (step S2). For example, the polymer precursor solution for forming a polymer may have a glass transition temperature (Tg) of 200 ° C or higher.

    The polymer precursor solution for forming a polymer may include a polymer precursor represented by the following formula (2).

(2)

In Formula 2,

Z ₁ can be one selected from a carbonyl group, a hydroxyl group, an amide group, a sulfonyl group, or a combination thereof;

Z ₂ can be a divalent organic group;

n ₁ may be an integer from 1,000 to 1,500,000.

Z ₂ in Formula 2 may include at least one member selected from the organic groups represented by Formulas 1-1 to 1-14, for example.

N ₁ in Formula 2 may be an integer of 10,000 to 500,000, for example.

The step of applying the polymer precursor solution for forming a polymer may include a doctor blade process. The doctor blade process can obtain a film having a precise thickness. In addition, the polymer precursor solution for forming a polymer can be used to increase the adhesiveness to the upper surface of the inorganic thin film. The thickness of the polymer film may be, for example, 1 占 퐉 to 10 占 퐉.

Next, the polymer precursor solution for polymer formation is cured to form a polymer film on the upper surface of the material thin film (step S3).

The step of forming the polymer film on the upper surface of the thin film may include a step of heat-treating the polymer precursor solution for polymer-forming at 50 ° C to 500 ° C or curing the polymer precursor solution by light treatment using visible light or ultraviolet light for 30 minutes to 24 hours have. The heat treatment may be performed for about 0.5 to 30 hours, but may be suitably controlled depending on the kind of the polymer precursor. The heat treatment may be performed in an air atmosphere or an oxidizing atmosphere.

The polymer precursor solution for forming a polymer may further contain a polymerization initiator. If necessary, a conductive agent, an emulsifying agent, a dispersing agent, or the like may be further added to the polymer precursor solution for forming a polymer.

Examples of the polymerization initiator include organic peroxides such as lauroyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate and 3,3,5-trimethylhexanoyl peroxide ; azo compounds such as?,? '- azobisisobutyronitrile; Ammonium persulfate; And potassium persulfate. One type of polymerization initiator may be used alone, or two or more types may be used in combination at an arbitrary ratio. However, there is no particular limitation on the examples of the polymerization initiator, and it is possible to use all polymerization initiators that can be used in the technical field.

The content of the polymerization initiator can be used in an amount usually used in thermal polymerization. In addition, additives such as amines can be used as polymerization auxiliary agents. Conducting agents, emulsifiers, or dispersants can also be used in amounts normally used in thermal polymerization.

The polymeric film formed on the upper surface of the thin film is separated from the substrate to produce the above-described flexible thermoelectric composite structure (step S4).

The method may further include the step of impregnating the polymer membrane formed on the upper surface of the material thin film with an aqueous solvent before being separated from the substrate.

The aqueous solvent may be water or alcohol-based. The alcohol-based solvent may be, for example, methanol, ethanol or propanol, and may be, for example, methanol. The step of impregnating the water-based solvent may further include the step of obtaining the above-described flexible thermoelectric composite article.

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only illustrative of the present invention, and the present invention is not limited to the following examples.

[Example]

Example  1: Manufacture of thermoelectric composite structure

Layered carbon nanotube (average diameter: about 10-15 nm, average length: about 0.5 to 10 μm) was coated on a substrate (thickness: 50 μm) of polar tetrafluoroethylene (PTFE) having pores of 0.2 μm A solution dispersed in 50 mL of ethanol was dropped, and an organic thin film having a thickness of about 20 mu m including multi-walled carbon nanotubes was coated on the substrate using a vacuum filtration method.

A polymer precursor solution for polymer formation to which 1 g of a polymer precursor containing a repeating unit represented by the formula (3) in the following Scheme 1 was added was placed on the top surface of the organic thin film in 10 ml of N-methyl-2-pyrrolidone (NMP) Using a blade.

The polymer precursor solution for polymer formation was cured by heat treatment at 100 ° C for 30 minutes in the atmosphere to form a polymer film represented by Chemical Formula 4 of the following reaction scheme 1 on the organic thin film. The thickness of the polymer film formed at this time was about 10 mu m.

The organic thin film and the polymer film formed on the top surface of the organic thin film were separated from the substrate to prepare a thermoelectric composite structure in which the multi-walled carbon nanotube thin film was localized on one surface of the polymer film.

In the above formula, n may be an integer of 1,000 to 1,000,000.

Comparative Example  1: Manufacture of thermoelectric composite structure

0.01 g of a multi-walled carbon nanotube (average diameter: 10-15 nm, average length: about 0.5 to 10 탆) and 0.1 g of a polymer precursor containing a repeating unit represented by the formula (3) - pyrrolidone (NMP) solvent.

The above dispersion was coated on a glass substrate (thickness: 1 mm) using a doctor blade.

The dispersion was cured by heating at 100 ° C for 30 minutes in the atmosphere to cure the polymer precursor containing the repeating unit represented by Chemical Formula 3 of the Reaction Scheme 1 to form multi-walled carbon nanotubes on the glass substrate, To form a composite membrane composed of a polymer represented by the following formula. The thickness of the composite film formed at this time was about 250 탆.

The composite membrane was separated from the substrate to prepare a thermocompression composite in which the multi-walled carbon nanotubes were dispersed in the composite membrane.

Analysis example  1: Scanning electron microscope ( SEM ) Image analysis

  The cross sections of the thermoelectric composite structures produced in Example 1 and Comparative Example 1 were observed using a scanning electron microscope (SEM). Here, JSM-7610F (operated at 5.0 kV) manufactured by JOEL, Ltd. was used for the SEM analysis. The results are shown in Fig. 4 and Fig. 5, respectively.

Referring to FIG. 4, it can be seen that the multi-walled carbon nanotube thin film is localized on one side of the polymer membrane in the thermoelectric composite structure manufactured in Example 1.

Referring to FIG. 5, it can be seen that the thermoelectric composite structure manufactured in Comparative Example 1 has multi-walled carbon nanotubes dispersed in the polymer and multi-walled carbon nanotube composite film.

Evaluation example  1: Evaluation of thermoelectric properties

    The thermoelectric properties including the electric conductivity, the Seeback coefficient, and the power factor of the thermocompression composite structure prepared in Example 1 and Comparative Example 1 were evaluated. The results are shown in Figs. 6 to 8, respectively.

The electrical conductivity (σ) was measured at 300 K by the conventional dc 4-probe method, and the Seebeck coefficient (S) was measured by the steady-state method. The power factor is calculated by multiplying the square of the electric conductivity and the Seebeck coefficient since it is S ² σ as described in Equation (1).

6 to 8, the thermocompression composite structure manufactured according to Example 1 has an electrical conductivity (σ) of 2330 ± 107 (S / m), a Seebeck coefficient (S) of 29.8 ± 0.5 (㎶ / K) And the power factor (S ² σ) is 2.06 ± 0.27 (㎼ / mK ² ). Comparative Example 1 The thermal transfer composite structure produced by the electric conductivity (σ) is 0.290 ± 0.115 (S / m) , Seebeck coefficient (S) is 25.9 ± 23.9 (㎶ / K) , and power factor (S ² σ) is 2.34 × 10 ^-4 ± 0.27 (㎼ / mK ² ).

From this, it can be confirmed that the electric conductivity () and the power factor (S ² σ) of the thermocompression composite structure produced in Example 1 were increased in comparison with the thermoelectric composite structure produced in Comparative Example 1.

1: flexible thermoelectric composite conductor, 2: inorganic thin film,
3: a polymer film having a glass transition temperature (Tg) of 200 DEG C or higher,

Claims (17)

A polymer membrane having a glass transition temperature (Tg) of 50 DEG C or higher; And
And a thin film coated on one side of the polymer membrane with a material having a Seebeck coefficient of 賊 1 kN / K or more. The method according to claim 1,
Wherein the thin film is an n-type or a p-type. The method according to claim 1,
Wherein the material is selected from organic, inorganic or organic complexes. The method of claim 3,
Wherein the organic material or the inorganic material is a one-dimensional nanomaterial. The method of claim 3,
The organic material is selected from a single layer wall or a multilayer wall carbon nanotube, a graphene, a polyacetylene polymer, a polypyrrole polymer, a polythiophene polymer, a polyaniline polymer, a polyphenylene sulfide polymer, and a polyphenylene oxide polymer At least one self - standing flexible thermoelectric composite structure. The method of claim 3,
Wherein the inorganic material is at least one selected from the group consisting of nanoparticles composed of a transition metal, a rare earth element, a group 13 element, a group 14 element, and a group 16 element, a nanowire, a nanowire, Flexible thermoelectric composite structure. The method according to claim 1,
Wherein the content of the material is 0.01 to 90 parts by weight based on 100 parts by weight of the thermoelectric composite structure. The method according to claim 1,
Wherein the polymer film is a self-supporting type film including at least one polymer selected from the group consisting of polyimide, polycarbonate, polyacrylate, polymethacrylate, polymethyl methacrylate, polyvinylidene, polyvinylidene fluoride, polystyrene, and urethane- Flexible thermoelectric composite structure. The method according to claim 1,
Wherein the polymer membrane comprises a polymer containing a repeating unit represented by the following formula (1): < EMI ID =
&Lt; Formula 1 &gt;

In Formula 1,
Y is a divalent organic group,
n is an integer of 1,000 to 1,500,000. 10. The method of claim 9,
Wherein Y in the formula (1) is at least one selected from organic groups represented by the following formulas (1-1) to (1-14):
&Lt; Formula 1-1 >< EMI ID =

&Lt; Chemical Formula 1-3 &gt;

&Lt; Formula 1-5 &gt;&lt; Formula 1-6 &gt;

&Lt; Formula 1-7 &gt;&lt; Formula 1-8 &gt;

&Lt; Formula 1-9 &gt;&lt; Formula 1-10 &gt;

&Lt; Formula 1-11 &gt;&lt; Formula 1-12 &

&Lt; Formula 1-13 &gt;&lt; Formula 1-14 &

A thermoelectric device comprising the self-contained flexible thermoelectric composite structure according to any one of claims 1 to 10. Coating a thin film of a material having a Seebeck coefficient of 1 1 / K or more on one side of the substrate;
Applying a polymer precursor solution for forming a polymer having a glass transition temperature (Tg) of 50 DEG C or higher on the upper surface of the thin film;
Forming a polymer film on the upper surface of the material thin film by curing the polymer precursor polymer precursor solution; And
And separating the polymer film formed on the upper surface of the thin film from the substrate to produce the self-sustaining flexible thermoelectric composite structure according to claim 1. The method of manufacturing the self-sustaining flexible thermoelectric composite structure according to claim 1, 13. The method of claim 12,
Wherein the step of coating the thin film having the Seebeck coefficient of at least 1 kPa is performed by a spin coating method, a doctor blade method, a vacuum filtration method, or a sedimentation method. 13. The method of claim 12,
Wherein the polymer precursor solution for polymer-forming comprises a polymer precursor repeating unit represented by the following general formula (2): < EMI ID =
(2)

In Formula 2,
Z ₁ is a group selected from a carbonyl group, a hydroxyl group, an amide group, a sulfonyl group, or a combination thereof;
Z ₂ is a divalent organic group;
n ₁ is an integer of 1,000 to 1,500,000. 13. The method of claim 12,
Wherein the step of applying the polymer precursor solution for polymer-forming comprises a doctor blade process. 13. The method of claim 12,
The step of forming the polymer film on the upper surface of the thin film may include a step of heat-treating the polymer precursor solution for polymer-forming at 50 ° C. to 500 ° C., or a step of curing the polymer precursor solution by light treatment using visible light or ultraviolet light for 30 minutes to 24 hours A method for manufacturing a flexible thermoelectric composite structure. 13. The method of claim 12,
Further comprising the step of impregnating the polymer film formed on the upper surface of the thin film material with an aqueous solvent before being separated from the substrate.

Images