JP2003046145A - Thermoelectric material, method of manufacturing the same and thermoelectric element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new thermoelectric material whose workability and thermoelectric characteristic are superior and which can obtain an n-type thermoelectric characteristic according to the characteristic of an inorganic thermoelectric material, to provide a thermoelectric element, and to provide a method of manufacturing the thermoelectric material. SOLUTION: In the thermoelectric material, an organic thermoelectric material and the inorganic thermoelectric material are integrated in a dispersion state, the organic thermoelectric material is selected from among polyaniline or its derivative, polypyrrole or its derivative, polythiophene or its derivative, a polyphenylene vinylene derivative, a polyparaphenylene derivative, a polyacene derivative and a copolymer of these material. The inorganic thermoelectric material is at least one kind selected from among a Bi-(Te,Se)-based material, an Si-Ge-based material, a Pb-Te-based material, a GeTe-AgSbTe-based material, a (Co,Ir,Ru)-Sb-based material, and a (Ca,Sr,Bi)Co2 O5 -based material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric material and a thermoelectric element used for thermoelectric power generation by the Seebeck effect, so-called thermoelectric conversion such as electronic cooling by the Peltier effect (direct conversion of energy without moving parts), and manufacturing thereof. Regarding the method, it is devised so that the organic polymer and the inorganic thermoelectric material are hybridized to have both the moldability of the organic polymer and the thermoelectric properties of the inorganic thermoelectric material.

[0002]

2. Description of the Related Art Thermoelectric conversion using thermoelectric conversion materials such as thermoelectric generation and electronic cooling has no moving parts that cause vibration, noise, wear, etc., has a simple structure, high reliability, long life and maintenance. It enables the production of a simplified energy direct conversion device that has the characteristic of being easy. For example, it is possible to directly obtain DC power without using various fossil fuels, etc., or to use a refrigerant. Suitable for temperature control.

By the way, in evaluating the characteristics of a thermoelectric conversion material, a physical internal factor T represented by the following equation:
PF and thermoelectric figure of merit ZT are used.

[0004]

[Equation 1]

[0005]

[Equation 2]

Here, S: Seebeck coefficient, σ: electrical conductivity, κ: thermal conductivity. In thermoelectric conversion materials, this Z
It is desired that T is large, that is, the Seebeck coefficient S is high, the electric conductivity σ is high, and the thermal conductivity κ is low.

For example, when the thermoelectric conversion material is used for thermoelectric power generation or the like, it is desirable that the thermoelectric conversion material has a high thermoelectric figure of merit of ZT = 0.02 or more and operates stably for a long period of time under a use environment. Be done. In addition, for mass-production of thermoelectric power generators for in-vehicle use or exhaust heat utilization, a material that has sufficient heat resistance and strength at high temperature and does not cause characteristic deterioration, and a manufacturing method that can efficiently produce this at low cost. Is desired.

Conventionally, P has been used as such a thermoelectric conversion material.
bTe or MSi ₂ (M: Cr, Mn, Fe, C
Silicide compounds such as o) and the like, and silicide-based materials such as a mixture thereof are used.

Further, TSb ₃ (T: Co, Ir, Ru)
Examples using Sb compounds such as, for example, thermoelectric materials obtained by adding impurities for determining the electric conductivity type to a material containing CoSb ₃ as a main component in the chemical composition have been reported (LD Dudkin and N.Kh. AbrikoSov. , Soviet Physics So
lid State Physics (1959) pp.126) BNZobrinaand, LD
Dudkin, Soviet Physics Solid State Physics (1960) p
p.1668) K. Matsubara, T. Iyanaga, T. Tsubouchi, K. Kish
imoto and T. Koyanagi, American Institute of Physics
(1995) pp.226-229).

As the inorganic thermoelectric material, Bi- (Te, Se) -based materials such as bismuth telluride, Si-Ge-based materials,
Pb-Te system, GeTe-AgSbTe system, (Ca, S
Various materials such as r, Bi) Co ₂ O ₅ system have been proposed and studied.

[0011]

The above-mentioned inorganic thermoelectric materials have been found to be high in practical use in terms of thermoelectric characteristics, but have the drawback that they are not easily processed.

For example, Japanese Unexamined Patent Publication (Kokai) No. 8-32124 discloses a method of manufacturing an ingot for manufacturing a thermoelectric conversion element and cutting the ingot to manufacture a rectangular parallelepiped thermoelectric conversion element. However, it is considered that the material loss is large and the yield is reduced due to cracking and chipping during cutting.

On the other hand, polyaniline has been studied as an organic thermoelectric material having good workability.

Further, a thermoelectric material composed of polyaniline which is an organic thermoelectric material and vanadium oxide has been proposed (E. Lazaro, M, Bhamidipati, M. Aldissi and B. Dixon,
AD Rep, pp1-35 (1998)), a thermoelectric material composed of polyaniline which is also an organic thermoelectric material, NaFeP type whiskers, and NaFeP type nanowires has been proposed. (J.Wa
ng et al. 20th International Conference on Thermoe
lectrics, pp352-355 (2001)).

However, none of them has a problem that they are inferior to the inorganic thermoelectric materials in terms of thermoelectric characteristics.

A thermoelectric material in which a metal powder such as silver, gold or platinum is dispersed in an organic thermoelectric material has been proposed (US Pat. No. 5,973,050).

However, what is shown here is
Only a thermoelectric material having a Seebeck coefficient of p type.

Generally, when an organic thermoelectric material is used, p
For example, when forming a Peltier element or the like, an n-type thermoelectric material made of the same material is required. Therefore, it is important to provide a thermoelectric material having N-type thermoelectric characteristics. .

In view of the above circumstances, the present invention is a novel thermoelectric material and thermoelectric material which have both processability and excellent thermoelectric characteristics and can obtain n-type thermoelectric characteristics depending on the characteristics of the inorganic thermoelectric material used. An object is to provide a method for manufacturing an element and a thermoelectric material.

[0020]

[Means for Solving the Problems] As a result of various researches for solving the above problems, as a result of hybridizing an organic thermoelectric material with an inorganic thermoelectric material by a predetermined method, the organic thermoelectric material is improved in workability. As a result, the inventors have found that a novel thermoelectric material that is excellent in terms of thermoelectric characteristics and that is excellent as an inorganic thermoelectric material and also exhibits n-type thermoelectric characteristics can be realized, and the present invention has been completed.

The first aspect of the present invention is selected from polyaniline or a derivative thereof, polypyrrole or a derivative thereof, polythiophene or a derivative thereof, polyphenylene vinylene derivative, polyparaphenylene derivative, polyacene derivative, and a copolymer of these materials. At least one type of organic thermoelectric material, and Bi- (T
e, Se) system, Si-Ge system, Pb-Te system, GeTe
-AgSbTe system, (Co, Ir, Ru) -Sb system,
A thermoelectric material characterized by being integrated with at least one inorganic thermoelectric material selected from the group consisting of (Ca, Sr, Bi) Co ₂ O ₅ in a dispersed state.

A second aspect of the present invention is the same as the first aspect, wherein the inorganic thermoelectric material has a particle size on the order of several hundreds μm or less, and the organic thermoelectric material is dissolved in an organic solvent. The thermoelectric material is formed by removing the organic solvent from a dispersion liquid in which the inorganic thermoelectric material is dispersed.

A third aspect of the present invention is the thermoelectric material according to the first or second aspect, which is characterized in that it is formed into a thin film.

A fourth aspect of the present invention is the thermoelectric material according to any one of the first to third aspects, characterized in that the thermoelectric material is formed in at least one layer of a multilayer film in which a plurality of thin films are laminated. is there.

A fifth aspect of the present invention is characterized in that, in any one of the first to fourth aspects, the inorganic thermoelectric material is dispersed while being surrounded by the organic thermoelectric material in the form of fine particles. It is in thermoelectric material.

In a sixth aspect of the present invention, in any one of the first to fifth aspects, the molar ratio of the organic thermoelectric material to the inorganic thermoelectric material is 1/99 or more. It is in.

A seventh aspect of the present invention is the thermoelectric material according to the sixth aspect, characterized in that the molar ratio of the organic thermoelectric material to the inorganic thermoelectric material is 1/99 to 91/9. .

An eighth aspect of the present invention is the thermoelectric material according to any one of the first to seventh aspects, characterized in that the thermoelectric material is integrated by being heat treated.

A ninth aspect of the present invention is the thermoelectric material according to the eighth aspect, wherein the heat treatment is performed at 50 ° C to 500 ° C.

A tenth aspect of the present invention is the thermoelectric material according to any one of the first to ninth aspects, characterized in that the thermoelectric figure of merit ZT is 0.02 or more.

An eleventh aspect of the present invention is any one of the first to fourth aspects, further comprising a plasticizer,
In addition, the thermoelectric material is characterized in that the inorganic thermoelectric material is integrated in a state of being in the form of fine particles and in close contact with each other.

The twelfth aspect of the present invention relates to the first to fourth and first aspects.
In any one aspect of 1, the thermoelectric material is characterized in that the inorganic thermoelectric material is 10 to 70 moles with respect to 1 mole of the organic thermoelectric material.

The thirteenth aspect of the present invention is the eleventh or twelfth aspect.
In the embodiment, the thermoelectric material is characterized in that the plasticizer is an ionic liquid.

In a fourteenth aspect of the present invention, in any one of the eleventh to thirteenth aspects, the plasticizer is contained in an amount of 0.01 to 0.2 mol based on 1 mol of the organic thermoelectric material. The thermoelectric material is characterized by.

The fifteenth aspect of the present invention is the first to fourth and eleventh aspects.
In any one of the modes 1 to 14, the inorganic thermoelectric material is
A thermoelectric material having a particle size of 50 μm or less.

The sixteenth aspect of the present invention is the first to fourth and eleventh aspects.
In any of the aspects 1 to 15, the inorganic thermoelectric material is
A thermoelectric material characterized by being treated with a titanate-based or silane-based surface treatment agent.

A seventeenth aspect of the present invention is a thermoelectric element using the thermoelectric material according to any one of the first to sixteenth aspects.

The eighteenth aspect of the present invention is to provide polyaniline or a derivative thereof, polypyrrole or a derivative thereof,
Polythiophene or a derivative thereof, a polyphenylene vinylene derivative, a polyparaphenylene derivative, a polyacene derivative, and an organic thermoelectric material solution in which at least a part of at least one organic thermoelectric material selected from a copolymer of these materials is dissolved, Bi- (Te, Se)
System, Si-Ge system, Pb-Te system, GeTe-AgSb
Te system, (Co, Ir, Ru) -Sb system, (Ca, S
r, Bi) A monolayer or multi-layered multi-layered thin film thermoelectric material is produced by applying a dispersion solution in which at least one inorganic thermoelectric material selected from the group consisting of Co ₂ O ₅ is dispersed. There is a method of manufacturing a thermoelectric material.

A nineteenth aspect of the present invention is the method for producing a thermoelectric material according to the eighteenth aspect, characterized in that the inorganic thermoelectric material has a particle size of 50 μm or less.

The twentieth aspect of the present invention is the eighteenth or nineteenth aspect.
In the aspect, the thermoelectric material manufacturing method is characterized in that the inorganic thermoelectric material is 10 to 70 moles with respect to 1 mole of the organic thermoelectric material.

A twenty-first aspect of the present invention is the method for producing a thermoelectric material according to any one of the eighteenth to twentieth aspects, which further comprises a plasticizer.

A twenty-second aspect of the present invention is the method for producing a thermoelectric material according to the twenty-first aspect, wherein the plasticizer is an ionic liquid.

The twenty-third aspect of the present invention is the twenty-first or twenty-second aspect.
In one aspect, the plasticizer is contained in an amount of 0.01 to 0.2 mol with respect to 1 mol of the organic thermoelectric material, in the method for producing a thermoelectric material.

A twenty-fourth aspect of the present invention is the method for producing a thermoelectric material according to any one of the eighteenth to twenty-third aspects, characterized in that the coating is performed by a method selected from casting, spin coating and dipping. is there.

In the present invention, the fine particles of the inorganic thermoelectric material are dispersed in a state of being surrounded by the organic thermoelectric material and are hybridized, probably because the fine particles of the inorganic thermoelectric material are arranged as a binder. It is integrated in the state of being electrically connected through, the workability is close to that of organic polymer material, and the thermoelectric property becomes excellent thermoelectric material like inorganic thermoelectric material,
It is also possible to obtain a thermoelectric material that exhibits N-type thermoelectric characteristics.

In the present invention, the organic thermoelectric material is an organic polymer having conductivity, but fine particles of an inorganic material can be integrated in an electrically conducting state. The hybrid material thus integrated is obtained by mixing the organic thermoelectric material and the inorganic thermoelectric material in a fine particle state and press-molding the mixture in a state where heat is applied as necessary, or the organic thermoelectric material is used in an organic solvent. It can be produced by uniformly dispersing fine particles of an inorganic thermoelectric material in a dissolved solution, applying the solution, and then removing the solvent. Preferably, the latter method is preferable, and therefore, the organic thermoelectric material is preferably one that dissolves in an organic solvent. Instead of the organic thermoelectric material, any organic polymer having no conductivity and soluble in an organic solvent can be used. When an organic polymer having no conductivity is used, it is necessary that the film thickness between the fine particles of the inorganic thermoelectric material is partly in the order of nm or less where the film thickness is small.

Examples of the organic thermoelectric material include polyaniline or its derivative, polypyrrole or its derivative, polythiophene or its derivative, polyphenylene vinylene derivative, polyparaphenylene derivative, polyacene derivative, and copolymers of these materials. , Especially polyaniline and polypyrrole,
It is preferable because it has excellent thermoelectric properties and is soluble in a solvent. In addition, polythiophene, polyphenylene vinylene,
Since polyparaphenylene and polyacene are extremely difficult to dissolve in a solvent, it is preferable to use a derivative having an alkyl group, a carboxylic acid group, a sulfonic acid group, or an ester thereof introduced therein. Note that these organic thermoelectric materials are doped with a dopant such as phosphoric acid, naphthalene sulfonic acid, toluene sulfonic acid, camphor sulfonic acid, if necessary.

The organic solvent that dissolves the organic thermoelectric material is not particularly limited as long as it dissolves the organic polymer. For example, when polyaniline or polypyrrole is used, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DM
F), m-cresol, toluene, xylene and the like can be used, and when a derivative of polyaniline, polypyrrole, polythiophene, polyphenylene vinylene, polyparaphenylene, polyacene is used, chlorobenzene, chloroform, tetrahydrofuran (T
HF) or the like can be used.

The dispersion solution in which the fine particles of the inorganic thermoelectric material are dispersed in the solution in which the organic thermoelectric material is dissolved in the organic solvent is in a stable state, probably because the fine particles of the inorganic thermoelectric material are surrounded by the organic polymer. Is dispersed in. In order to obtain such a stable dispersed state, the surrounding force of the organic polymer,
It is preferable to select a material which is influenced by the compatibility of the inorganic thermoelectric material with the organic polymer solution, the specific gravity, and the like and which can obtain a stable dispersed state.

When such a compatible material is selected, the inorganic thermoelectric material may have a particle size of the order of several hundreds of μm, but when the compatibility is not so good, The particle size is preferably in the order of 100 μm to nm.

It is also possible to add an additive for assisting the dispersion of the fine particles of the inorganic thermoelectric material, such as a surfactant, to prepare a dispersion solution.

By using such a dispersion solution, a hybrid thermoelectric material in a thin film state can be easily produced. That is, a thin film thermoelectric material can be easily manufactured by applying a dispersion solution in which an inorganic thermoelectric material is dispersed in an organic polymer solution.

On the other hand, the inorganic thermoelectric material that can be used in the present invention is not particularly limited, and conventionally known or later discovered inorganic thermoelectric materials can be used. For example, Bi- (Te, Se) -based materials can be used. , Si-Ge system, Pb-T
e system, GeTe-AgSbTe system, (Co, Ir, R
u) -Sb system, and the like _{(Ca, Sr, Bi) Co} 2 O 5 system.

Here, in order to remarkably exhibit the characteristics of the organic thermoelectric material, the molar ratio of the organic thermoelectric material to the inorganic thermoelectric material is set to, for example, 1/99 or more. 1
If it is less than / 99, it is considered that the effect of using the organic polymer cannot be remarkably exhibited. In particular, the molar ratio of the organic thermoelectric material to the inorganic thermoelectric material is 1/99 to 91 /
It can be used in a range of 9. This is because the fine particles of the inorganic thermoelectric material can be electrically conducted to each other, and the advantage of high workability due to the incorporation of the organic thermoelectric material can be obtained.

On the other hand, when the characteristics of the organic thermoelectric material are not remarkably exhibited and only the workability of the inorganic thermoelectric material is improved, 10 to 70 moles of the inorganic thermoelectric material are used with respect to 1 mole of the organic thermoelectric material. Is preferred. A thin film thermoelectric conversion material can be easily manufactured by applying the dispersion solution prepared by such a formulation.

In this case, it is preferable to improve the solubility of the organic thermoelectric material by using a plasticizer. The plasticizer is not particularly limited, but since conductivity can be added,
It is preferable to use an ionic liquid.

Here, the ionic liquid is a molten salt which is a liquid at room temperature, and is also called a room temperature molten salt, and particularly has a melting point of 70 ° C. or lower, preferably 30 ° C. or lower. Such an ionic liquid has properties such as no vapor pressure (nonvolatile), high heat resistance, nonflammability, and chemical stability.

The ionic liquid is, for example, imidazolium.
Cyclic amidine ion such as ion, pyridinium ion
Ion, ammonium ion, sulfonium ion, phospho
Using organic cations such as nickel ions as cations
Is. As the anion, AlCl_Four ^-, Al_TwoCl
₇ ^-, NO_Three ^-, BF_Four ^-, PF₆ ^-, CH_ThreeCOO^-, C
F _ThreeCOO^-, CF_ThreeSO_Three ^-, (CF_ThreeSO_Two)
_TwoN^-, (CF_ThreeSO_Two)_ThreeC^-Can be mentioned
It In addition, as a more specific example,
A combination of an organic cation and a counter anion represented by the following formula
We can mention the ones made from a combination.

[0059]

[Chemical 1]

[0060]

[Chemical 2]

In the present invention, an ionic liquid compatible with the organic thermoelectric material may be used, and there is no particular limitation. Although the amount of the ionic liquid used is not limited, it can be used in an amount of about 0.01 to 0.2 mol per mol of the organic thermoelectric material.

As described above, in the present invention, the dispersion solution in which the fine particles of the inorganic thermoelectric material are dispersed in the organic thermoelectric material solution is used,
Conventionally, it is possible to easily realize a thin film form that cannot be obtained by the inorganic thermoelectric material. Further, by such thinning, a multilayer film in which the same thin films are laminated, a multilayer film in which an organic thermoelectric material and a hybrid material are alternately laminated, an organic thermoelectric material film or a hybrid film in which an organic thermoelectric material is doped Various configurations such as a multilayer film in which an organic thermoelectric material film without doping or a hybrid film are combined with each other can be realized.

As a method for forming such a thin film,
Although not particularly limited, casting, spin coating, dipping and the like can be cited as examples.

A thin film can be obtained by removing the organic solvent by drying after coating by such a method, but in some cases, heat treatment may be performed thereafter. Such heat treatment is performed at, for example, 50 ° C to 12
It is carried out at 00 ° C, preferably 50 ° C to 500 ° C.

By such heat treatment, the organic polymer may be burned or lost, and the crystal structure of the inorganic thermoelectric material may be changed depending on the case, whereby the thermoelectric material is densified and the thermoelectric characteristics are improved. It

According to the present invention described above, the thermoelectric figure of merit ZT, which cannot be easily realized by the conventional organic thermoelectric material, is used.
Of 0.02 or more can be realized, the workability is good, and a thin film that cannot be realized by an inorganic thermoelectric material can be realized, and thus it is promising as a new thermoelectric material.

Further, by using the thermoelectric material of the present invention, a thermoelectric element having good thermoelectric characteristics can be easily manufactured, and so-called thermoelectric conversion such as thermoelectric power generation by the Seebeck effect and electronic cooling by the Peltier effect can be performed. It can be used for (direct conversion of energy without moving parts).

[0068]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on Examples.

Example 1 Polyaniline (PANi)
0.505 g and camphor sulfonic acid (CSA) 0.
Mix 586 g well in an agate mortar and screw this.
Transfer to a tube and add 24.835 g of m-cresol,
After sonication (50 ° C, 4h), centrifuge to conduct electricity
A polyaniline solution was obtained. This solution has a molar ratio of PANi
/ Bi_TwoTe _ThreeBismuth telluride to be 1/1
Add (agate mortar and mashed for 5 minutes) and add agate mortar
Mix well and cast on a silicon wafer substrate
It was The cast film was vacuum dried (60 ° C., overnight).
When this film is observed by SEM, the bismuth telluride becomes uniform.
It was a dense and dispersed film.

(Example 2) PANi / Bi ₂ Te ₃ = 1
A hybrid film was formed in the same manner as in Example 1 except that /3.2 was used. When this film was observed by SEM, it was a dense film in which bismuth telluride was uniformly dispersed.

Example 3 The film of Example 2 was further heat treated under the following conditions.

After setting the sample and flowing nitrogen for 10 minutes,
The temperature was raised from room temperature to 500 ° C. at 5 ° C./min in nitrogen (200 mL / min), and the temperature was kept at 500 ° C. for 30 minutes.
Then, it was naturally cooled to room temperature. When the film thus heat-treated was observed by SEM, the shape of the film was not changed.

(Test Example 1) The hybrid films of Examples 2 and 3 were set in a thermoelectromotive force measuring device, and their thermoelectric properties were measured. As a result, all exhibited n-type thermoelectric properties, and although the conductivity of the film after the heat treatment of Example 3 was hardly changed, the Seebeck coefficient was dramatically increased.

Further, as shown in FIG. 1, the physical internal factor TPF (S ² σ) is much higher than that before the heat treatment,
Further, the thermoelectric figure of merit ZT reached a maximum of 0.2 even though it was not doped with bismuth telluride.

Example 4 Polyaniline (PANi)
0.030 g and camphor sulfonic acid (CSA) 0.
Mix well with 035g in agate mortar, transfer to a screw tube, m-cresol 0.63g, EMITFS
I 0.012g and ultrasonic treatment (50 ° C, 3h)
After that, a polyaniline solution was obtained. 0.032g of this solution
To the above, 0.263 g of Co _0.9 Pt _0.1 Sb ₃ was added and mixed. A sample was prepared by applying this to a ceramic plate.

In this case, PANi, EMI
FSI, Co_0.9Pt_0.1Sb _ThreeThe molar ratio of PA
Ni: EMITFSI: Co_0.9Pt_0.1Sb_Three=
It becomes 1: 0.09: 41.6.

(Example 5) Conductive polyaniline of Example 4
To 0.013 g of the solution, Co_0.9Pt_0.1Sb _ThreeTo
0.144g was added and mixed. This is a ceramic plate
To prepare a sample.

In this case, PANi, EMI
FSI, Co_0.9Pt_0.1Sb _ThreeThe molar ratio of PA
Ni: EMITFSI: Co_0.9Pt_0.1Sb_Three=
It becomes 1: 0.09: 62.5.

Comparative Example 1 Polyaniline (PANi)
0.025 g and camphor sulfonic acid (CSA) 0.
The mixture was thoroughly mixed with 029 g in an agate mortar, transferred to a screw tube, 2.48 g of m-cresol was added, and ultrasonic treatment (50 ° C., 3 h) was performed to obtain a polyaniline solution. The film obtained by removing the solvent was used as a test sample.

Comparative Example 2 Polyaniline (PANi)
0.051 g and camphor sulfonic acid (CSA) 0.
Mix well with 059 g in an agate mortar, transfer to a screw tube, 2.48 g of m-cresol, EMITFS
I0.02g and ultrasonic treatment (50 ° C, 3h)
After that, a polyaniline solution was obtained. The film obtained by removing the solvent was used as a test sample.

In this case, PANi, EMI
The FSI molar ratio is PANi: EMITFSI = 1: 1.
It becomes 0.09.

(Comparative Example 3) Co _0.9 Pt _0.1 Sb ₃ was added to 0.103 g of the polyaniline solution obtained in Comparative Example 1.
0.098 g was added and mixed. A sample was prepared by applying this to a ceramic plate.

In this case, PANi, Co
The molar ratio of _0.9 Pt _0.1 Sb ₃ is PANi: Co.
It becomes _0.9 Pt _0.1 Sb ₃ = 1: 20.4.

(Comparative Example 4) Co _0.9 Pt _0.1 Sb ₃ was added to 0.055 g of the polyaniline solution obtained in Comparative Example 1.
0.105 g was added and mixed. A sample was prepared by applying this to a ceramic plate.

In this case, PANi, Co
The molar ratio of _0.9 Pt _0.1 Sb ₃ is PANi: Co.
It becomes _0.9 Pt _0.1 Sb ₃ = 1: 41.0.

(Comparative Example 5) As an inorganic thermoelectric material, Co was used.
A bulk of _0.9 Pt _0.1 Sb ₃ was used as a sample for Comparative Example 5.

(Comparative Example 6) As an inorganic thermoelectric material, a bulk of Co _0.9 Pt _0.1 Sb ₃ of Comparative Example 5 was crushed and then molded into a pellet by a handy press.
Used as a sample.

(Test Example 2) Samples of Examples 4 and 5,
The samples of Comparative Examples 1 to 6 were set in a thermoelectric measuring device, and the Seebeck coefficient thereof was measured. The result is shown in FIG.

The workability of Examples 4 and 5 and Comparative Examples 1 to 6 was evaluated as ◯ when a thin film could be formed by the coating method and as x when it could not be formed. The results are shown in Table 1.

As a result, as shown in FIG.
5, that is, the test samples in which the inorganic thermoelectric material and the ionic liquid were mixed in the organic thermoelectric material all showed n-type thermoelectric characteristics, and Comparative Example 1: a sample made of only the organic thermoelectric material, Comparative Example 2 : Compared with a sample in which only an ionic liquid is added to an organic thermoelectric material, Comparative Examples 3 and 4: a sample in which only an inorganic thermoelectric material is added to an organic thermoelectric material, Comparative Examples 5 and 6: a sample including only an inorganic thermoelectric material It has become clear that it shows a close Seebeck coefficient.

Further, since Examples 4 and 5 contained the organic thermoelectric material, they were found to be excellent in workability as compared with the samples made of only the inorganic thermoelectric material such as Comparative Examples 5 and 6. It was

Thus, by adding the inorganic thermoelectric material and the ionic liquid to the organic thermoelectric material, a thermoelectric material having a large Seebeck coefficient and high processability could be obtained.

[0093]

[Table 1]

[0094]

As described above, according to the present invention,
A novel thermoelectric material that hybridizes an organic thermoelectric material and an inorganic thermoelectric material to have both the processability of the organic thermoelectric material and the thermoelectric characteristics of the inorganic thermoelectric material and also obtains n-type thermoelectric characteristics according to the characteristics of the inorganic thermoelectric material. The material can be realized.

[Brief description of drawings]

FIG. 1 is a physical intrinsic factor TP of Examples 2 and 3 of the present invention.
It is a graph which shows F and thermoelectric figure of merit ZT.

FIG. 2 is a graph showing Seebeck coefficients of Examples 4 and 5 of the present invention and Comparative Examples 1 to 6.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01L 35/34 H01L 35/34 H02N 11/00 H02N 11/00 A (72) Inventor Kosuke Kamei Nakamura, Niihama, Ehime Prefecture 2-chome 2438-5 (72) Inventor Akinori Tsubata 2-3-6, Shirute, Tsurumi-ku, Yokohama-shi, Kanagawa Kitatsunaga Kogyo Co., Ltd. (72) Takashi Tokuda 2-3-6, Shirute, Tsurumi-ku, Yokohama-shi, Kanagawa Issue Hokushin Kogyo Co., Ltd. F-term (reference) 4J002 CE001 CM011 CM021 CN001 DC006 DE096 FD206 GQ00

Claims (24)

[Claims] 1. An organic thermoelectric material which is at least one selected from polyaniline or a derivative thereof, polypyrrole or a derivative thereof, polythiophene or a derivative thereof, polyphenylene vinylene derivative, polyparaphenylene derivative, polyacene derivative, and a copolymer of these materials. Material, Bi- (Te, Se) system, Si-Ge system,
Pb-Te system, GeTe-AgSbTe system, (Co, I
r, Ru) -Sb system, (Ca, Sr, Bi) Co 2 O 5
A thermoelectric material, characterized in that it is integrated with at least one inorganic thermoelectric material selected from the system in a dispersed state. 2. The dispersion according to claim 1, wherein the inorganic thermoelectric material has a particle size of several hundreds μm order or less, and the inorganic thermoelectric material is dispersed in a solution in which the organic thermoelectric material is dissolved in an organic solvent. A thermoelectric material, which is formed by removing the organic solvent from a liquid. 3. The thermoelectric material according to claim 1, which is formed in a thin film shape. 4. The thermoelectric material according to claim 1, wherein the thermoelectric material is formed on at least one layer of a multilayer film in which a plurality of thin films are laminated. 5. The thermoelectric material according to claim 1, wherein the inorganic thermoelectric material is dispersed in a fine particle state so as to be surrounded by the organic thermoelectric material. 6. The molar ratio of the organic thermoelectric material to the inorganic thermoelectric material according to any one of claims 1 to 5,
A thermoelectric material characterized by being 99 or more. 7. The molar ratio of the organic thermoelectric material to the inorganic thermoelectric material according to claim 6, wherein the molar ratio is 1/99 to 91 /
9. A thermoelectric material characterized by being 9. 8. The thermoelectric material according to claim 1, which is integrated by being heat treated. 9. The heat treatment according to claim 8, wherein the heat treatment is 50 ° C.
A thermoelectric material, characterized in that it was performed at ˜500 ° C. 10. The thermoelectric material according to claim 1, which has a thermoelectric figure of merit ZT of 0.02 or more. 11. The method according to any one of claims 1 to 4, further comprising a plasticizer, and the inorganic thermoelectric materials are integrated in a state of being in close contact with each other in a fine particle state. Thermoelectric material. 12. The thermoelectric material according to any one of claims 1 to 4 and 11, wherein the inorganic thermoelectric material is 10 to 70 moles with respect to 1 mole of the organic thermoelectric material. 13. The thermoelectric material according to claim 11 or 12, wherein the plasticizer is an ionic liquid. 14. The method according to any one of claims 11 to 13,
The plasticizer is 0.0 with respect to 1 mol of the organic thermoelectric material.
A thermoelectric material containing 1 to 0.2 mol. 15. The thermoelectric material according to any one of claims 1 to 4 and 11 to 14, wherein the inorganic thermoelectric material has a particle size of 50 μm or less. 16. The thermoelectric material according to any one of claims 1 to 4 and 11 to 15, wherein the inorganic thermoelectric material is treated with a titanate-based or silane-based surface treatment agent. 17. A thermoelectric element comprising the thermoelectric material according to claim 1. 18. An organic thermoelectric material which is at least one selected from polyaniline or its derivative, polypyrrole or its derivative, polythiophene or its derivative, polyphenylene vinylene derivative, polyparaphenylene derivative, polyacene derivative, and a copolymer of these materials. In the organic thermoelectric material solution in which at least a part of the material is dissolved, Bi- (Te, Se) system, Si-Ge system, Pb
-Te system, GeTe-AgSbTe system, (Co, Ir,
Ru) -Sb system and (Ca, Sr, Bi) Co ₂ O ₅ system, at least one kind of inorganic thermoelectric material is dispersed to apply a dispersion solution to form a single layer or a multi-layered thin film of two or more layers. A method for producing a thermoelectric material, which comprises producing a thermoelectric material. 19. The method for producing a thermoelectric material according to claim 18, wherein the inorganic thermoelectric material has a particle diameter of 50 μm or less. 20. The inorganic thermoelectric material according to claim 18 or 19, wherein 1 mol of the organic thermoelectric material contains 10 to 7 parts of the inorganic thermoelectric material.
A method for producing a thermoelectric material, characterized in that the amount is 0 mol. 21. In any one of claims 18 to 20,
Furthermore, the manufacturing method of the thermoelectric material characterized by containing a plasticizer. 22. The method for manufacturing a thermoelectric material according to claim 21, wherein the plasticizer is an ionic liquid. 23. The plasticizer according to claim 21, wherein the plasticizer is 0.01 to 1 mol with respect to 1 mol of the organic thermoelectric material.
A method for producing a thermoelectric material, which comprises 0.2 mol. 24. In any one of claims 18 to 23,
The method for producing a thermoelectric material, wherein the coating is performed by a method selected from casting, spin coating, and dipping.