KR102353622B1 - Polymer thermoelectric material comprising gold nanoparticles - Google Patents

Abstract

The present invention provides a polymer thermoelectric material comprising gold (Au) nanoparticles, wherein the material comprises a polythiophene-based conjugated polymer matrix and Au nanoparticles doped with Au ions, thereby effectively improving thermoelectric properties, which have been insufficient in the prior art, and realizing excellent doping stability. The present invention is expected to be actively utilized as a wearable device or a flexible thermoelectric element by applying the polymer thermoelectric material.

Description

Polymer thermoelectric material containing gold (Au) nanoparticles {POLYMER THERMOELECTRIC MATERIAL COMPRISING GOLD NANOPARTICLES}

The present invention relates to a polymer thermoelectric material including gold (Au) nanoparticles. Specifically, it relates to a polymer thermoelectric material having excellent doping stability and excellent thermoelectric properties by including a polythiophene-based conjugated polymer matrix doped with Au ions and Au nanoparticles.

As for thermoelectric materials, research on inorganic materials with excellent thermoelectric performance such as _{Bi 2} Te _{3 has been the focus.} However, since most of the inorganic thermoelectric materials with good efficiency are rare elements, their price is high and their brittleness and flexibility are insufficient, so that their application to various industrial fields is limited.

On the other hand, organic materials are cheaper than inorganic materials and can be deposited over a large area, and have excellent toughness, elasticity, and low thermal conductivity. In addition, since the process cost can be reduced by applying a solution process and a hybrid thermoelectric material can be manufactured by mixing with various materials, research on thermoelectric materials using organic materials has been actively conducted in recent years.

As a representative organic material, a conjugated polymer with high electrical conductivity is used. Examples include polypyrole (PPY), polyaniline (PANI), polycarbazole, polythiophene (PTh), poly(3,4-ethlyenedioxythiophene) (PEDOT) and poly(4-styrene). sulfonic acid) (PSS) and the like. These conjugated polymers have very poor solubility in solvents, making the manufacturing process difficult, but in the case of Poly(3-hexylthiophene) (P3HT), when doped, it has excellent electrical conductivity and is soluble in various organic solvents, so it has been widely studied as a thermoelectric material. is becoming

However, according to the reported papers and the like, it is pointed out that the thermoelectric properties of P3HT are relatively inferior to those of other conductive polymers. the current situation.

An object of the present invention to solve the above problems is to provide a polymer thermoelectric material comprising a polythiophene-based conjugated polymer matrix doped with Au ions and Au nanoparticles.

Another object of the present invention is to provide a thermoelectric device including the above-described polymer thermoelectric material and having excellent thermoelectric performance.

As a result of many studies to achieve the above object, in the case of a polythiophene-based conjugated polymer matrix doped with Au ions and a polymer thermoelectric material containing Au nanoparticles, it was found that it has remarkable doping stability and excellent thermoelectric properties. The invention was completed.

The present invention provides a polymer thermoelectric material comprising a polythiophene-based conjugated polymer matrix doped with Au ions and Au nanoparticles, wherein the Au nanoparticles are uniformly dispersed and impregnated in the polymer matrix.

According to an embodiment of the present invention, the Au ions may be _{AuCl 4} ^-.

According to an embodiment of the present invention, the X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material may have Au peaks at 84.2±0.5, 86.8±0.5, 87.8±0.5 and 90.3±0.5 eV.

According to an embodiment of the present invention, an X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material may have Cl peaks at 198.5±0.5 and 200.0±0.5 eV.

According to an embodiment of the present invention, the Au ions and Au nanoparticles may be located on the surface of the polymer matrix.

According to an embodiment of the present invention, the average particle diameter of the Au nanoparticles may be 1 to 5 nm.

According to an embodiment of the present invention, the Au nanoparticles may be formed from _{the AuCl 4} ^-.

According to an embodiment of the present invention, in the polymer thermoelectric material, a peak in the 500±1 nm region in the UV-vis spectrum may satisfy Equation 1 below.

[Equation 1] I ₈₀₀ /I _i ≤ 1.1

(In Equation 1, I _i is the peak intensity in the 500±1 nm region in the UV-vis spectrum of the polymer thermoelectric material measured immediately after doping, and I ₈₀₀ is the polymer thermoelectric material measured after doping and left for 800 hours. It is the peak intensity in the 500±1nm region in the UV-vis spectrum.)

According to an embodiment of the present invention, electrical conductivity (S/cm) of the polymer thermoelectric material may satisfy Equation 2 below.

[Equation 2] E ₃₀₀ /E _i ≥ 0.3

(In Equation 2, E _i is the electrical conductivity of the thermoelectric element manufactured using the polymer thermoelectric material measured immediately after doping, and E ₃₀₀ is the thermoelectric material manufactured using the polymer thermoelectric material measured 300 hours after doping. It is the electrical conductivity of the device.)

According to an embodiment of the present invention, the polymer thermoelectric material may have a thickness of 10 to 100 nm.

The present invention provides a thermoelectric material array including the above-described polymer thermoelectric material; and an electrode electrically connecting the thermoelectric material array.

The present invention comprises the steps of preparing a polythiophene-based conjugated polymer film; applying the polythiophene-based conjugated polymer film with a doping solution containing AuCl _{3 ;} and Au ions are partially reduced to form Au nanoparticles.

According to an embodiment of the present invention, the polythiophene-based conjugated polymer film may be prepared by heat treatment at a temperature of 120° C. or higher.

According to an embodiment of the present invention, the doping solution may contain AuCl ₃ at a concentration of 2 to 10 mM.

Since the polymer thermoelectric material according to the present invention contains Au ions and Au nanoparticles at the same time, it is possible to effectively improve thermoelectric properties, which were insufficient in the prior art, and to realize excellent doping stability. By applying the polymer thermoelectric material, it is expected to be actively utilized as a wearable device or a flexible thermoelectric element.

1 is an X-ray photoelectron spectroscopy (XPS) Au4f and Cl2p spectrum of the surface of a polymer thermoelectric material according to Example 3. FIG.
2 is a GIWAXS two-dimensional image of a polymer thermoelectric material prepared in Examples and Comparative Examples.
3 is a TEM image of a polymer thermoelectric material prepared in Examples and Comparative Examples. Specifically, (a) is an undoped P3HT film (top view), (b) is a polymer thermoelectric material of Comparative Example 5 (top view), (c) is a polymer thermoelectric material of Example 5 (top view) view), (d) is a TEM image of the polymer thermoelectric material of Comparative Example 4 (cross-sectional), and (e) is a TEM image of the polymer thermoelectric material (cross-sectional) of Example 3.
4 is a UV-vis spectrum (A) measured immediately after doping of the polymer thermoelectric material prepared in Examples and Comparative Examples, and UV-vis spectrum (B) measured after exposure to the air for 800 hours after doping.
5 is a polymer thermoelectric device prepared in Examples 6, 12, 18, 24, 30 and Comparative Examples 12, 18, 24, and 30.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

In addition, in the present specification, the unit used without special mention is based on the weight, for example, the unit of % or ratio means weight % or weight ratio, and unless otherwise defined, the weight % is the composition of any one component of the entire composition. It means % by weight in

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

Also, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

In addition, the numerical range used herein includes the lower limit and upper limit and all values within the range, increments logically derived from the form and width of the defined range, all values defined therein, and the upper limit of the numerical range defined in different forms. and all possible combinations of lower limits. Unless otherwise defined in the specification of the present invention, values outside the numerical range that may occur due to experimental errors or rounding of values are also included in the defined numerical range.

Hereinafter, a polymer thermoelectric material including gold (Au) nanoparticles according to an embodiment of the present invention will be described in more detail.

The present invention provides a polymer thermoelectric material comprising a polythiophene-based conjugated polymer matrix (hereinafter referred to as a polymer matrix) doped with Au ions and Au nanoparticles, wherein the Au nanoparticles are uniformly dispersed in the polymer matrix. characterized in that

The polymer matrix may be prepared by doping a polythiophene-based conjugated polymer with Au ions, and the polythiophene-based conjugated polymer is P3HT (poly(3-hexylthiophene)), PDPPT (poly(diketopyrrolopyrrole) -terteopene)), P3BT (poly(3-butylthiophene)), P3OT (poly(3-octylthiophene)), P3DDT (poly(3-dodecylthiophene)), etc. can be used, preferably P3HT (poly(3-hexylthiophene)) may be used.

According to an embodiment of the present invention, the Au ion may be used without limitation as long as it is an Au ion capable of doping the polythiophene-based conjugated polymer, and may be AuX ₄ ^- (X = halogen), preferably AuCl ₄ ^- can be. The Au ions may be ionized by a conventional and well-known method, and specifically, may be ionized through reduction and Lewis acid reaction in the doping process. However, when the polythiophene-based conjugated polymer is doped with Fe ions, the doping effect is remarkably deteriorated over time, which is not preferable because stable thermoelectric properties cannot be realized.

According to an embodiment of the present invention, the Au ions may be located on the surface of the polymer matrix, or located both on the surface and inside, to dope the polythiophene-based conjugated polymer. The polymer matrix is doped with P-type, and the polymer thermoelectric material including the same may be a P-type thermoelectric material. The P-type thermoelectric material may further include an electrode to manufacture a thermoelectric element. When a thermoelectric element is manufactured including the polymer thermoelectric material according to an embodiment of the present invention, it is preferable because it has excellent doping stability and thus excellent thermoelectric performance can be expressed for a long time.

According to an embodiment of the present invention, the Au nanoparticles may be located on the surface of the polymer matrix, specifically, the surface and the inside, and specifically located between the polymer crystal structures of the polymer matrix. have. Since the Au nanoparticles are positioned between the polymer crystal structures, the electrical conductivity and doping stability of the polymer matrix can be remarkably improved, and the thermoelectric properties of the polymer thermoelectric material including the Au nanoparticles can be effectively improved. In addition, the average particle diameter of the Au nanoparticles may be 0.1 to 10 nm, specifically 1 to 5 nm, more specifically 2 to 3 nm, in the case of a polymer thermoelectric material containing Au nanoparticles satisfying the above range, Excellent thermoelectric properties can be realized.

According to an embodiment of the present invention, the Au nanoparticles may be formed after preparing a doped polythiophene-based conjugated polymer matrix by doping the polythiophene-based conjugated polymer. Specifically, it may be formed from the Au ions, and more specifically, it may be formed from _{AuCl 4} ^{− .} More specifically, a portion of the Au ions may be reduced to form the Au nanoparticles.

According to an embodiment of the present invention, the X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material may have Au peaks at 84.2±0.5, 86.8±0.5, 87.8±0.5 and 90.3±0.5 eV. The peaks at the 86.8±0.5 (Au ³⁺ _{Au4f 7/2} ) and 90.3±0.5 (Au ³⁺ Au4f _5/2 ^{) eV can confirm the presence of Au 3+ that} is an Au ion, and the 84.2±0.5 (Au4f _7/2 ) and 87.8±0.5 (Au4f _5/2 ) eV peaks can confirm the presence of Au nanoparticles. The presence of the Au ions and Au nanoparticles was confirmed by analyzing the Au4f spectrum obtained through the X-ray photoelectron spectroscopy (XPS).

According to an embodiment of the present invention, the X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material shows the peaks of Cl ions at _{198.5±0.5 (Cl2p 3/2} ) and 200.0±0.5 (Cl2p _{1/2) eV.} can have The peaks at 86.8±0.5 and 90.3±0.5 eV can confirm the presence of Cl ions, and the Cl2p spectrum obtained through the X-ray photoelectron spectroscopy (XPS) was analyzed.

Due to the influence of Au nanoparticles located between the crystalline structures of the polymer matrix, the crystal plane of the polymer thermoelectric material according to an embodiment of the present invention may change when compared to the crystal plane of the undoped polythiophene-based conjugated polymer. This change in the crystal plane can be confirmed through surface crystal analysis, for example, through GIWAXS (Grazing Incidence Wide Angle X-ray Scattering) analysis.

According to an embodiment of the present invention, the peak intensity of the polymer thermoelectric material in the 500±1 nm region in the UV-vis spectrum may be reduced than that of the undoped polythiophene-based conjugated polymer. In general, the peak in the 500±1 nm region is a neutral state peak, which means that the polymer is not doped, and the peak in the 800±5 nm region is a polaron-bipolaron state peak, which means that the polymer is doped. When the doping property of the doped polymer thermoelectric material was analyzed based on the peak intensity of the region, the polymer thermoelectric material according to an embodiment of the present invention was 500 in the UV-vis spectrum compared to the undoped polythiophene-based conjugated polymer. As the peak intensity in the ±1nm region is reduced by 30% or more, specifically by 60% or more, effective thermoelectric properties can be realized. Preferably, in the polymer thermoelectric material, a peak intensity in the 800±5 nm region in the UV-vis spectrum measured immediately after doping may be higher than the peak intensity in the 500±1 nm region, which is the polymer thermoelectric material according to an embodiment of the present invention. It may mean that the material has excellent doping efficiency.

The polymer thermoelectric material according to an embodiment of the present invention may satisfy Equation 1, specifically Equation 3 below.

[Equation 1] I ₈₀₀ /I _i ≤ 1.1

[Equation 3] I ₈₀₀ /I _i ≤ 1.05

(In Equations 1 and 4, I _i is the peak intensity in the 500±1 nm region in the UV-vis spectrum of the polymer thermoelectric material measured immediately after doping, and I ₈₀₀ is the polymer measured after doping and leaving for 800 hours. It is the peak intensity in the 500±1nm region in the UV-vis spectrum of the thermoelectric material.)

In the case of a polymer thermoelectric material satisfying Equation 1, specifically Equation 3, the doping effect can be maintained for a long time, and excellent doping stability and excellent thermoelectric properties can be realized. In addition, it is possible to manufacture a thermoelectric device having excellent doping stability and thermoelectric properties using the same.

In general, thermoelectric performance evaluation of thermoelectric materials uses a dimensionless figure of merit called ZT, which can be expressed as follows.

ZT=S ² σT/κ

Here, S is the Seebeck coefficient, indicating the potential difference due to the temperature difference, σ is electrical conductivity, T is absolute temperature, and κ is thermal conductivity. It can be said that the higher the ZT value, the better the thermoelectric performance. However, since it is very difficult and difficult to measure the thermal conductivity of a thin film, thermoelectric performance is evaluated using only the ^{power factor (S 2 σ).}

According to an embodiment of the present invention, the polymer thermoelectric material may have an electrical conductivity measured immediately after doping of 15 S/cm or more, specifically 50 S/cm or more, and more specifically 200 S/cm or more. In the case of a polymer thermoelectric material satisfying the above range, a thermoelectric device having excellent thermoelectric performance can be manufactured. In addition, the polymer thermoelectric material according to an embodiment of the present invention may have electrical conductivity (S/cm) satisfying Equation 2 below.

[Equation 2] E ₃₀₀ /E _i ≥ 0.3

[Equation 4] E ₃₀₀ /E _i ≥ 0.5

(In Equation 2, E _i is the electrical conductivity of the thermoelectric element manufactured using the polymer thermoelectric material measured immediately after doping, and E ₃₀₀ is the thermoelectric material manufactured using the polymer thermoelectric material measured 300 hours after doping. It is the electrical conductivity of the device.)

Satisfying Equation 2 means that the electrical conductivity of a thermoelectric element manufactured using a polymer thermoelectric material measured immediately after doping is maintained at 30% or more, and satisfying Equation 4 is 50 % or more. Preferably, the electrical conductivity of the thermoelectric device manufactured using the polymer thermoelectric material according to an embodiment of the present invention may be maintained at 70% or more after 300 hours based on immediately after doping. A polymer thermoelectric material satisfying Equation 2, specifically Equation 4, exhibits excellent doping stability, and a thermoelectric device manufactured using the same is preferable because excellent thermoelectric properties can be realized.

According to one embodiment of the present invention, the polymeric material may be at least one thermoelectric power factor (Power Factor) The 40μW / K ¹ m ² or more, for example 70 μW / K ¹ m ² measured immediately after doping. In the case of a polymer thermoelectric material satisfying the above range, a thermoelectric device having excellent thermoelectric performance can be manufactured.

According to an embodiment of the present invention, the polymer thermoelectric material may have a thickness of 5 to 350 nm, specifically 10 to 200 nm, and more specifically 10 to 100 nm, but is not limited thereto and depends on the final product to be manufactured. The thickness can be adjusted.

The present invention may provide a thermoelectric device including the above-described polymer thermoelectric material. The thermoelectric element may have a conventional or known structure, and may include a thermoelectric material array including the above-described polymer thermoelectric material, which is specifically a P-type thermoelectric material; and an electrode electrically connecting the thermoelectric material array. If necessary, it may further include a contact thermal conductor layer, a filling material for filling the empty space between the thermoelectric material array, and the like. As the electrode, gold (Au), aluminum (Al), ITO (indium-tin oxide)), IZO (indium zinc oxide), silver (Ag), etc. may be used, and specifically gold may be used, but is not limited thereto. .

Hereinafter, a method for manufacturing a polymer thermoelectric material including gold (Au) nanoparticles according to an embodiment of the present invention will be described in more detail.

The present invention comprises the steps of preparing a polythiophene-based conjugated polymer film; applying the polythiophene-based conjugated polymer film with a doping solution containing AuCl _{3 ;} and Au ions are partially reduced to form Au nanoparticles. Specific descriptions of the raw material used in the manufacturing method and the manufactured polymer thermoelectric material and examples of compounds are the same as described above, and thus will be omitted.

The step of preparing the polythiophene-based conjugated polymer film is to prepare a polymer solution by dissolving the polythiophene-based conjugated polymer in a solvent to prepare a film. Specifically, the solvent can be used without limitation as long as it can dissolve the polythiophene-based conjugated polymer, and is not limited as long as it is commonly used or known, for example, chlorobenzene may be used. The concentration of the polymer solution may be 0.1 to 10% by weight or 1 to 5% by weight, but the concentration may be adjusted according to the thickness of the film to be prepared. The process for preparing the polymer solution into a film may be conventionally used or may be prepared according to a known method, and a spin coating method may be used as a non-limiting example. The coated polymer solution may be dried to prepare a film, but is not limited thereto.

Then, the prepared polythiophene-based conjugated polymer film may be further subjected to a heat treatment step. Specifically, it may be prepared by heat treatment at a temperature of 120 °C or higher, specifically 130 to 170 °C, more specifically 140 to 160 °C. When the heat treatment is performed in the above temperature range, the degree of crystallinity of the polymer of the prepared polythiophene-based conjugated polymer film may be increased, and thus, a polymer thermoelectric material having further improved doping efficiency and doping stability may be manufactured.

Next, a step of preparing a doping solution and applying it to the film may be performed. Specifically, the doping solution _{may be a solution containing AuX 3} (X=halogen) and a solvent capable of dissolving it, and AuX ₃ (X=halogen) may be specifically AuCl ₃ .

The solvent is commonly used or known in the doping solution and _{can be used without much limitation as long as it can dissolve AuX 3} (X = halogen), for example, nitromethane or acetonitrile, etc. can be used. can

According to an embodiment of the present invention, the doping solution may contain AuCl ₃ at a concentration of 0.1 to 20 mM, specifically 1 to 15 mM, more specifically 2 to 10 mM, or 2 to 6 mM. When the polymer thermoelectric material is manufactured using a doping solution satisfying the above range, excellent doping stability can be effectively implemented and optimal thermoelectric performance can be exhibited. In addition, it is very preferable because it is possible to manufacture a thermoelectric element exhibiting remarkable thermoelectric performance by using the same.

The doping solution may be conventionally used or applied to the polythiophene-based conjugated polymer film by a known method, and non-limiting examples include, but not limited to, an impregnation method, a spin coating method, or a SqP method. does not

After the doping solution is applied, a polythiophene-based conjugated polymer film doped with _{AuCl 3 as a dopant can be prepared through the following steps.}

_{a) Reduction of AuCl 3} in polythiophene-based conjugated polymer [AuCl ₃ (aq) + e ^- -> AuCl ₂ + Cl ^- ]

b) Lewis acid reaction [AuCl ₃ (aq) + Cl ^- -> AuCl ₄ ^- ]

c) Doping process of positively charged polythiophene-based conjugated polymer and AuCl ₄ ^{− and}

d) AuCl ₄ ^- partial reduction process of ^{_{[AuCl 4 - + 3e - -}} > Au nanoparticle;

Through steps a) to d), AuCl ₄ ^- A polymer thermoelectric material including a polythiophene-based conjugated polymer matrix doped with and Au nanoparticles can be prepared. Specifically, by preparing the Au nanoparticles in step d), the crystal domain arrangement of the polythiophene-based conjugated polymer may become disordered. Furthermore, as the concentration of the doping solution increases, the disorder may increase. Accordingly, it is possible to manufacture a polymer thermoelectric material and a thermoelectric device having improved doping stability and excellent thermoelectric performance.

Hereinafter, a polymer thermoelectric material including gold (Au) nanoparticles according to the present invention and a method for manufacturing the same will be described in more detail through examples. However, the following examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

[Examples 1 to 5]

A polymer solution containing P3HT (poly(3-hexylthiophene)) in chlorobenzene at a concentration of 2% by weight was prepared and spin-coated to prepare a P3HT film with a thickness of 50 nm, and heat-treated at 150° C. for 1 hour. A doping solution containing AuCl ₃ at concentrations of 0.5, 1, 2.5, 5 and 10 mM in acetonitrile was spin-coated on the P3HT film to finally prepare a polymer thermoelectric material.

[Comparative Examples 1 to 5]

In the above example, FeCl _{3 was used instead of AuCl 3} to prepare a doping solution, and the same procedure as in Example was performed.

UV-vis, XPS and GIWAXS analysis was performed on the polymer thermoelectric materials prepared in Examples and Comparative Examples. The Au4f and Cl2p spectra obtained by X-ray photoelectron spectroscopy (XPS) of the surface of the polymer thermoelectric material according to Example 3 are shown in FIG. 1 . As shown in FIG. 1, by confirming the 84.2 and 87.8 eV peaks in the Au4f spectrum, the presence of Au nanoparticles was confirmed, and at the same time, 86.8 and 90.3eV peaks in the Au4f spectrum and 198.5 and 200.0 ± eV peaks in the Cl2p spectrum were confirmed. The presence of Au ions was also confirmed. In addition, GIWAXS (Grazing Incidence Wide Angle X-ray Scattering) analysis was performed to analyze the crystal structure of the prepared polymer thermoelectric material, and TEM analysis was performed to analyze the microstructure of the prepared polymer thermoelectric material surface. The two-dimensional image of the GIWAXS is shown in FIG. 2 and the TEM image is shown in FIG. 3 . Through the examples, the polymer thermoelectric material according to an embodiment of the present invention contains Au ions and Au nanoparticles at the same time, thereby changing the crystal structure of P3HT, a polymer matrix, to have improved doping efficiency, and furthermore, excellent doping stability. was able to confirm

For the polymer thermoelectric materials prepared according to Examples and Comparative Examples, UV-vis spectrum measured immediately after doping (A) and UV-vis spectrum measured after exposure to air for 800 hours after doping (B) is shown in FIG. 4 . As shown in FIG. 4 , _{the polymer thermoelectric materials of Examples 1 to 5 using AuCl 3} showed remarkably excellent doping stability even after 800 hours, and in particular, when a doping solution having a concentration of 2.5 mM or higher was used, more excellent doping stability was achieved. confirmed to have

[Examples 6 to 35]

In order to evaluate the thermoelectric performance, the polymer thermoelectric material prepared in Example above was used as a P-type thermoelectric material, and a 3 mm diameter gold electrode was thermally deposited on the thermoelectric material to prepare a unit thermoelectric element. At this time, the deposited two gold electrodes were separated by a distance of 15 mm, and the temperature gradient between the two electrodes was changed to 1 to 10 °C. 5 shows the manufactured thermoelectric element. In addition, after exposing the polymer thermoelectric material prepared in the above Example to the atmosphere for 24, 48, 96, 144, and 300 hours in the atmosphere according to the conditions shown in Table 1 below, a thermoelectric element was manufactured by the same manufacturing method and the physical properties were evaluated.

[Comparative Examples 6 to 35]

In Example 6, a thermoelectric element was manufactured in the same manner as in Example 6, except that the polymer thermoelectric material prepared in Comparative Example, not Example, was used. In addition, after exposing the polymer thermoelectric material prepared in the comparative example to the atmosphere for 24, 48, 96, 144, and 300 hours according to the conditions shown in Table 2 below, a thermoelectric element was manufactured by the same manufacturing method as above and the physical properties were evaluated.

Electrical conductivity was measured by the standard van der Pauwe direct current four-probe method, and Seebeck coefficient was measured from the slope of the linear junction of ΔV/ΔT. ^{In addition, the power factor (S 2} σ) was calculated using the electrical conductivity (σ) and the Seebeck coefficient (S), and is shown in Tables 1 and 2 below.

polymer
thermoelectric material atmospheric exposure time Electrical Conductivity
(S/cm) Seebeck Coefficient
(μV/K) Power Factor
(μW/m ¹ K ² ) Example 6 Example 1
(AuCl ₃ , 0.5 mM) 0 hours 16.1 163 42.5 Example 7 24 hours 13.6 169 38.8 Example 8 48 hours 13.1 171 33.5 Example 9 96 hours 11.1 160 32.5 Example 10 144 hours 10.0 171 27.4 Example 11 300 hr 5.9 187 20.6 Example 12 Example 2
(AuCl ₃ , 1 mM)
0 hours 54.8 120 78.9 Example 13 24 hours 56.5 116 76.0 Example 14 48 hours 58.1 118 72.9 Example 15 96 hours 58.2 112 81.0 Example 16 144 hours 52.1 121 75.8 Example 17 300 hr 42.0 132 73.2 Example 18 Example 3
(AuCl ₃ , 2.5 mM)


0 hours 207 73.9 110 Example 19 24 hours 207 75.9 119 Example 20 48 hours 202 72.2 105 Example 21 96 hours 209 72.1 109 Example 22 144 hours 196 74.4 105 Example 23 300 hr 164 75.3 93 Example 24 Example 4
(AuCl ₃ , 5 mM)


0 hours 313 48.0 72.1 Example 25 24 hours 290 49.9 72.2 Example 26 48 hours 276 53.3 67.9 Example 27 96 hours 265 49.6 75.3 Example 28 144 hours 256 57.0 80.6 Example 29 300 hr 225 54.5 66.8 Example 30 Example 5
(AuCl ₃ , 10 mM)

0 hours 272 34.0 31.4 Example 31 24 hours 249 38.8 37.5 Example 32 48 hours 229 42.2 37.7 Example 33 96 hours 211 40.6 37.6 Example 34 144 hours 197 46.8 36.4 Example 35 300 hr 148 76.7 81.7

polymer
thermoelectric material atmospheric exposure time Electrical Conductivity
(S/cm) Seebeck Coefficient
(μV/K) Power Factor
(μW/m ¹ K ² ) Comparative Example 6 Comparative Example 1
(FeCl ₃ , 0.5 mM)


0 hours N/A N/A N/A Comparative Example 7 24 hours N/A N/A N/A Comparative Example 8 48 hours N/A N/A N/A Comparative Example 9 96 hours N/A N/A N/A Comparative Example 10 144 hours N/A N/A N/A Comparative Example 11 300 hr N/A N/A N/A Comparative Example 12 Comparative Example 2
(FeCl ₃ , 1 mM) 0 hours 0.45 314 4.44 Comparative Example 13 24 hours 0.23 312 2.20 Comparative Example 14 48 hours 0.15 313 1.47 Comparative Example 15 96 hours 0.094 N/A N/A Comparative Example 16 144 hours 0.065 N/A N/A Comparative Example 17 300 hr 0.023 N/A N/A Comparative Example 18 Comparative Example 3
(FeCl ₃ , 2.5 mM) 0 hours 13.7 190 49.5 Comparative Example 19 24 hours 9.82 195 37.3 Comparative Example 20 48 hours 6.81 199 27.0 Comparative Example 21 96 hours 4.62 207 19.8 Comparative Example 22 144 hours 3.00 235 16.6 Comparative Example 23 300 hr 1.60 254 10.3 Comparative Example 24 Comparative Example 4
(FeCl ₃ , 5 mM) 0 hours 84.7 113 108.0 Comparative Example 25 24 hours 51.8 123 78.4 Comparative Example 26 48 hours 39.3 139 75.9 Comparative Example 27 96 hours 28.6 148 62.6 Comparative Example 28 144 hours 19.0 158 47.4 Comparative Example 29 300 hr 5.6 176 21.5 Comparative Example 30 Comparative Example 5
(FeCl ₃ , 10 mM) 0 hours 154.0 73 83.9 Comparative Example 31 24 hours 105.0 108 122.0 Comparative Example 32 48 hours 70.8 111 85.7 Comparative Example 33 96 hours 49.1 126 78.0 Comparative Example 34 144 hours 30.6 138 58.3 Comparative Example 35 300 hr 12.6 175 38.6

As shown in Tables 1 and 2, it was confirmed that the thermoelectric performance of the thermoelectric device manufactured using the polymer thermoelectric material manufactured according to an embodiment of the present invention was very excellent. In particular, Examples 18 to 23 using the polymer thermoelectric material of Example 3 showed the best thermoelectric properties (power factor), and even if left in the air for 300 hours, electrical conductivity was maintained at 79% based on immediately after doping. , it was possible to confirm the remarkable doping efficiency and doping stability of the polymer thermoelectric material according to the present invention. Although the preferred embodiments of the present invention have been described above, the present invention can use various changes, modifications and equivalents, and It is clear that the example can be applied with appropriate modifications. Accordingly, the above description is not intended to limit the scope of the present invention, which is defined by the limits of the following claims.

Claims (14)

A polymer thermoelectric material comprising a polythiophene-based conjugated polymer matrix doped with Au ions and Au nanoparticles, wherein the Au nanoparticles are uniformly dispersed and impregnated in the polymer matrix. The method of claim 1,
The Au ions are AuCl ₄ ^- Polymer thermoelectric material. The method of claim 1,
The X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material is a polymer thermoelectric material having Au peaks at 84.2±0.5, 86.8±0.5, 87.8±0.5 and 90.3±0.5 eV. The method of claim 1,
The X-ray photoelectron spectroscopy (XPS) spectrum of the surface of the polymer thermoelectric material has Cl peaks at 198.5±0.5 and 200.0±0.5 eV. The method of claim 1,
The Au ions and Au nanoparticles are polymer thermoelectric material located on the surface of the polymer matrix. The method of claim 1,
A polymer thermoelectric material having an average particle diameter of the Au nanoparticles of 1 to 5 nm. The method of claim 1,
The Au nanoparticles are AuCl ₄ ^{- A} polymer thermoelectric material formed from. The method of claim 1,
The polymer thermoelectric material is a polymer thermoelectric material in which a peak in the 500 ± 1 nm region in the UV-vis spectrum satisfies Equation 1 below.
[Equation 1]
I ₈₀₀ /I _i ≤ 1.1
(In Equation 1, I _i is the peak intensity in the 500±1 nm region in the UV-vis spectrum of the polymer thermoelectric material measured immediately after doping, and I ₈₀₀ is the polymer thermoelectric material measured after doping and left for 800 hours. It is the peak intensity in the 500±1nm region in the UV-vis spectrum.) The method of claim 1,
The polymer thermoelectric material has electrical conductivity (S/cm) satisfying Equation 2 below.
[Equation 2]
E ₃₀₀ /E _i ≥ 0.3
(In Equation 2, E _i is the electrical conductivity of the thermoelectric element manufactured using the polymer thermoelectric material measured immediately after doping, and E ₃₀₀ is the thermoelectric material manufactured using the polymer thermoelectric material measured 300 hours after doping. It is the electrical conductivity of the device.) The method of claim 1,
The polymer thermoelectric material has a thickness of 10 to 100 nm. A thermoelectric material array comprising the polymer thermoelectric material according to any one of claims 1 to 10; and an electrode electrically connecting the thermoelectric material array. Preparing a polythiophene-based conjugated polymer film;
applying the polythiophene-based conjugated polymer film with a doping solution containing AuCl _{3 ;} and
A method of manufacturing a polymer thermoelectric material comprising a; Au ions are partially reduced to form Au nanoparticles. 13. The method of claim 12,
The polythiophene-based conjugated polymer film is a method of manufacturing a polymer thermoelectric material prepared by heat treatment at a temperature of 120 ℃ or more. 13. The method of claim 12,
The doping solution is AuCl _{3 A} method for producing a polymer thermoelectric material comprising a concentration of 2 to 10 mM.

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