WO2017082578A1 - P-type skutterudite thermoelectric material, manufacturing method therefor, and thermoelectric element comprising same - Google Patents

Abstract

The present invention relates to a P-type skutterudite thermoelectric material, a manufacturing method therefor, and a thermoelectric element comprising the same. More specifically, the present invention relates to: a P-type skutterudite thermoelectric material having a specific filler material and charge compensating material, which are introduced therein, so as to exhibit high thermoelectric performance; a manufacturing method therefor; and a thermoelectric element.

Description

 【Specification】

 [Name of invention]

 p-type scrutherite thermoelectric material, manufacturing method thereof and thermoelectric element including the same

Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0158244 dated November 11, 2015 and Korean Patent Application No. 10-2016-0133019 dated October 13, 2016. All content disclosed in the literature is included as part of this specification.

 The present invention relates to a P-type scutterrudite thermoelectric material, a method for manufacturing the same, and a thermoelectric element including the same, and more particularly, to a P-type scuderudite thermoelectric material exhibiting high thermoelectric performance by introducing a specific filler and a charge compensation material. It relates to a manufacturing method and a thermoelectric element thereof.

[Technique to become background of invention]

 Recently, due to resource depletion and environmental problems caused by combustion, research on thermoelectric materials using waste heat as one of alternative energy is being accelerated.

 The energy conversion efficiency of these thermoelectric materials is the performance index value of the thermoelectric material

Depends on ZT Here ZT is determined according to Seebeck coefficient, electrical conductivity and thermal conductivity, and more specifically, is proportional to the square of the Seebeck coefficient and electrical conductivity, and inversely proportional to thermal conductivity. Therefore, in order to increase the energy conversion efficiency of the thermoelectric conversion element, it is necessary to develop a thermoelectric conversion material having a high Seebeck coefficient or high electrical conductivity or low thermal conductivity.

 Generally, the unit lattice should be large, complex crystal structure, heavy atomic mass, strong covalent bonds, large effective carrier mass, and high carrier mobility to have good thermoelectric performance. Narrow conditions, small differences in electronegativity between constituent atoms, etc. are required. In the case of Skutterudi te, narrow energy bands ¾ and high

1 Alternative paper (Article 26) Due to the charge transport speed, it is expected to be the most promising thermoelectric material in the long-range application of the medium silver range of 500 to 900K.

 However, skutterudi te exhibits low efficiency thermoelectric performance due to relatively high lattice thermal conductivity. In order to improve this problem, the lattice thermal conductivity is reduced by laminating a filler in two voids present in the scrudedite unit grid to induce a rattling effect. In addition, a method of improving the thermoelectric performance index by controlling a hole carrier concentration by inducing a part of an element with a doping element and inducing lattice scattering has been proposed.

 However, most studies are limited to N-type scrutherite and have been reported to improve the ZT performance index of N-type scrutherite through single or multi-pore filling. The results of the study are relatively insignificant, and the thermoelectric properties are lower than those of N-type filled screutite. Therefore, the development of P-type scrutherite thermoelectric materials having excellent thermoelectric performance remains a significant problem.

[Content of invention]

 Problem to be solved

 An object of the present invention is to provide a P-type scudrudite thermoelectric material having excellent thermoelectric performance.

 In addition, the present invention is to provide a method for producing the P-type scrutherite thermoelectric material.

 Moreover, this invention is providing the thermoelectric element containing the said P-type scrutherite thermoelectric material.

[Measures of problem]

 The present invention provides a P-type scuderudite thermoelectric material represented by the following formula (1).

In addition, the present invention is a raw material of Fe, Co and Sb, and at least two kinds of raw materials selected from the group consisting of Ce, La, Sm, Nd, Yb, In and Ba and Sn, Ge, Melting a mixture comprising at least one raw material selected from the group consisting of Se and Te; Cooling the molten mixture to form an ingot; Annealing the ingot; Grinding the ingot into powder; And sintering the powder; provides a method for producing a P-type scrutherite thermoelectric material comprising a.

 Moreover, this invention provides the thermoelectric element containing the said P-type scruterite thermoelectric material.

 Hereinafter, a P-type scuderudite thermoelectric material, a method of manufacturing the same, and a thermoelectric element including the same according to a specific embodiment of the present invention will be described in detail. According to one embodiment of the invention, there may be provided a P-type scrutherite thermoelectric material represented by the following formula (1):

 [Formula 1]

M _x Fe ₄ -yCoySbi2- _z H _z

 In Chemical Formula 1,

 M is at least two elements selected from the group consisting of Ce, La, Sm, Nd, Yb, In and Ba,

 H is at least one element selected from the group consisting of Sn, Ge, Se and Te,

 0 <χ <1.

 0 <y <4

 0 <z <12.

The present inventors have conducted research on P-type scrutherite thermoelectric materials having excellent thermoelectric performance, and are made of Ce, La, Sm, Nd, Yb, In, and Ba as fillers in P-type scutterrudite thermoelectric materials. When multi-filling two or more elements selected from, and doping a specific charge compensation material on Fe and Sb sites, the experiment shows that the lattice thermal conductivity is lowered and the output factor is increased to show high thermoelectric conversion efficiency. The invention has been completed. More specifically, two voids are present in the unit grid of the P-type scutterudite thermoelectric material, and when the fillers represented by M in the above formulas are layered, the rattling is performed. By reducing the lattice thermal conductivity and supplying additional electrons to change the hole carrier concentration. As described above, the P-type scudrudite thermoelectric material having reduced lattice thermal conductivity and improved output factor may exhibit more improved thermoelectric characteristics.

 In this case, as the filler (multi-layered two or more selected from the group consisting of Ce, La, Sni, Nd, Yb, In, and Ba), the thermoelectric properties improved compared to the case of using one type of filler The thermoelectric material which has is provided. And, more preferably, the filler may be multi-filled two or more selected from the group consisting of Nd, Ce, and Yb, specifically Nd and Ce multi-filled, Nd and Yb multi-filled, or Ce And Yb can be multi-layered.

 In addition, the P-type scutterrudite thermoelectric material is doped with a Co charge compensation material in the Fe site, the y value in the formula (1) represents the doping amount of Co doped in the Fe site, a value in the range of 0 <y <4 Has In particular, when the doping amount y of Co exceeds 1.5, the hole carrier concentration decreases according to the X and z values, which may cause a problem of deterioration of the P-type characteristics. In order to adjust the concentration, the y value is preferably 0 <y ≦ 1.5.

 In addition, the P-type scriberite thermoelectric material is doped with a specific charge compensation material represented by H in the formula (1), as well as Fe site, Sb site. In this case, H is at least one member selected from the group consisting of Sn, Ge, Se, and Te, and the doping amount z of H doped at Sb has a value in the range of 0 <z <12. In particular, when the doping amount z value of H exceeds 0.2, since the thermoelectric properties may be reduced by the formation of the secondary phase, it is preferable that 0 <z≤0.2.

As such, the P-type scudrudite thermoelectric material doped not only with Fe but also with Sb is doped with a specific charge compensation material to control the hole carrier concentration. It can optimize and reduce the lattice thermal conductivity to have a higher thermoelectric performance index ZT value.

 In particular, it is preferable to use Sn or Te as the charge compensation material doped at the Sb site, which can provide one additional hole for Sn and one for Te in the P-type scutterudite thermoelectric material. This is because additional electrons can be provided, so that the hole carrier concentration can be controlled and optimized by using the Sn: or Te appropriately alone or in combination.

In addition, specific examples of the P-type scrutherite thermoelectric material represented by Chemical Formula 1 may include Nd ₀ . ₄ Ce ₀ . ₄ Fe ₃ . o Coi. ₀ Sbn. ₉ Sn ₀ . i, Nd ₀ . ₄ Yb _{0. 4} Fe ₃ . ₀ Coi. ₀ Sbn. ₉ Sn ₀ . i, and Ceo. bo. _A Fes.oCoLoSbn.gSncu etc. are mentioned.

 On the other hand, according to another embodiment of the invention, raw materials of Fe, Co and Sb, and at least two kinds of raw materials selected from the group consisting of Ce, La, Sm, Nd, Yb, In and Ba and Sn, Ge, Melting a mixture comprising at least one raw material selected from the group consisting of Se and Te;

 Engraving the molten mixture to form an ingot;

 Annealing the ingot;

 Grinding the ingot into powder; And

 Sintering the powder; may be provided a method for producing a P-type scuterudite thermoelectric material comprising a.

 As described above, the present inventors have conducted research on a P-type scrutherite thermoelectric material having excellent thermoelectric performance, and the P-type scrutherite thermoelectric material manufactured by the above method is Ce, La, Sm, Including two or more selected from the group consisting of Nd, Yb, In and Ba as a layering material, doped with a specific charge compensation material in Fe and Sb sites, the lattice thermal conductivity and high output factor, improved thermoelectric conversion efficiency It was confirmed through the experiments.

More specifically, from the raw material of Fe, Co and Sb, two or more raw materials selected from the group consisting of Ce, La, Sm, Nd, Yb, In and Ba and Sn, Ge, Se and Te One or more selected raw materials are stoichiometrically weighed and mixed, charged in a quartz tube, and then The mixture may be melted. In this case, in order to prevent reaction between the raw material and the quartz tube, the mixture may be first put into a carbon crucible and then charged into the quartz tube.

In addition, the mixture may be melted at a temperature of about 950 to 1200 ^° C. in a vacuum and sealed quartz tube.

 Next, the molten mixture is engraved to form an ingot. The angle of inclination includes a natural angle, angle of inclination using a medium, and the like, and the angle of angle used in the field of thermoelectric materials may be applied without limitation.

And, the ingot may be annealed at about 400 to 800 ^° C for 10 to 200 hours.

 Next, the annealed ingot may be pulverized into a powder, in which case the powder may be pulverized to have a particle diameter of 100 urn or less, and the pulverization method and apparatus may be applied without limitation to methods and apparatuses used in the field of thermoelectric materials. Can be.

Then, the pulverized powder may be sintered. The sintering may be performed at a temperature of about 500 to 700 ^° C. using a spark plasma sintering method, and the sintering time is preferably 5 to 60 minutes at a pressure of 10 to 100 MPa. On the other hand, according to another embodiment of the present invention, a thermoelectric device including the P-type scrutherite thermoelectric material of the above-described embodiment may be provided.

 As described above, since the P-type scriberiteite thermoelectric material of the embodiment has a low lattice thermal conductivity, a high output factor, and an improved thermoelectric conversion efficiency, the thermoelectric element including the P-type scutterrudite thermoelectric material also has a high thermoelectric performance index ZT value. It can be usefully applied to future technology fields that can utilize the device for thermoelectric power generation.

【Effects of the Invention】 According to the present invention, a specific filler and a charge compensation material may be introduced to provide a P-type scrutherite thermoelectric material having excellent thermoelectric performance, a method of manufacturing the same, and a thermoelectric device including the same. [Brief Description of Drawings]

 1 is a result of X D analysis of the sciderrudite prepared in Examples and Comparative Examples.

 Figure 2 is a graph showing the electrical conductivity of the Scudrudite prepared in Examples and Comparative Examples.

 Figure 3 is a graph showing the Seebeck coefficient of the Scuterrudite prepared in Examples and Comparative Examples.

 Figure 4 is a graph showing the power factor (power factor) of the sciderrudite prepared in Examples and Comparative Examples.

 FIG. 5 is a graph showing the total thermal conductivity of the scudrudite prepared in Examples and Comparative Examples. FIG.

 FIG. 6 is a graph showing lattice thermal conductivity of scutterrudite prepared in Examples and Comparative Examples. FIG.

 7 is a graph showing the thermoelectric performance index (ZT) of the Scudrudite prepared in Examples and Comparative Examples.

[Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. Example 1: _Ndo.4Ceo. 4Fe3 _. oCcn.oSbu _. Manufacture of 9Sri。 j

 High-purity raw materials Nd, Ce, Fe, Co, Sb and Sn from glove boxes

The weight was measured at a molar ratio of 0.4: 0.4: 3: 1: 11.9: 0.1 and placed in a carbon crucible, which was then charged into a quartz tube. The inside of the quartz tube was vacuumed and sealed. And melting the raw material in llCXrC for 24 hours Constant temperature was maintained inside the furnace. Next, the quartz tube was naturally engraved at room temperature to form an ingot, and then annealed by maintaining the temperature constant at 650 ° C. for 72 hours in a f _urnace . The annealed ingot material was finely ground into a powder having a particle diameter of 75 or less, and sintered under a discharge plasma sintering method (SPS) for 10 minutes at a pressure of 50 MPa and a temperature of 630 ° C. to prepare a P-type scutterudite thermoelectric material It was.

 P-type scuterudite thermoelectric material in the same manner as in Example 1 except that high purity raw materials Nd, Yb, Fe, Co, Sb and Sn were used in a molar ratio of 0.4: 0.4: 3: 1: 11.9: 0.1 Example 3 Preparation of Ce ^ Yb Fe ^ Co ^ Sb ^ Sn ^

 P-type scrutherite thermoelectric in the same manner as in Example 1, except that the high purity raw materials Ce, Yb, Fe, Co, Sb and Sn were used in a molar ratio of 0.4: 0.4: 3: 1: 11.9: 0.1 Materials were prepared Comparative Example 1: Preparation of Nd ^ Ce ^ Fe Co ^ Sb

 A P-type scuderudite thermoelectric material was manufactured in the same manner as in Example 1, except that high purity raw materials Nd, Ce, Fe, Co, and Sb were used in a molar ratio of 0.4: 0.4: 3: 1: 12. . Comparative Example 2: Preparation of ^ ^?

A P-type scuderudite thermoelectric material was manufactured in the same manner as in Example 1, except that high purity raw materials Nd, Yb, Fe, Co, and Sb were used in a molar ratio of 0.4: 0.4: 3: 1: 12. . Comparative Example 3: Preparation of Ce Yb ^ Fe (^ ^ A P-type scudrudite thermoelectric material was manufactured in the same manner as in Example 1, except that the high purity raw materials Ce, Yb, Fe, Co, and Sb were used in a molar ratio of 0.4: 0.4: 3: 1: 12. . Comparative Example 4: Preparation of Ce ^ Fe ^ Co _j Sb Sn ^

A P-type scuderudite thermoelectric material was manufactured in the same manner as in Example 1, except that high purity raw materials Ce, Fe, Co, Sb, and Sn were used in a molar ratio of 0.8: 3: 1: 11.9: 0.1. . Comparative Example 5: Preparation of N gFe Co _jjj Sb ^ Sn ^

A P-type scuderudite thermoelectric material was manufactured in the same manner as in Example 1, except that high purity raw materials Nd, Fe, Co, Sb, and Sn were used in a molar ratio of 0.8: 3: 1: 11.9: 0.1. .

 A P-type scuderudite thermoelectric material was manufactured in the same manner as in Example 1, except that Yb, Fe, Co, Sb, and Sn, which were high purity raw materials, were used in a molar ratio of 0.8: 3: 1: 11.9: 0.1. . Experimental Example

 1. Phase analysis according to XRD pattern

 The P-type Scudrudite thermoelectric materials prepared in Examples and Comparative Examples are shown in FIG. 1 by phase analysis using an X-ray diffraction analyzer (XRD).

(A), (c) and (e) of FIG. 1 each represent Nd ₀ . ₄ Ce ₀ . ₄ Fe ₃ CoSb ₁₂ , Nd ₀ . ₄ Yb ₀ . _{4 Fe 3 CoSb 12, Ce 0} .4Ybo.4Fe 3 will showing the comparison examples 1, 2 and 3 of the analysis result having a composition of CoSbi2, (b), (d ), (f) , respectively

Ndo. bo _. Fes Co Sbu _. gSno. Ceo. ^ Bo FesCoSbn ^ Sno. The analysis results of Examples 1, 2 and 3 having the composition of (g), (h) and (i) are Ceo.sFesCoSbn.gSno.i and Ndo.sFeaCoSbu _. gSno _. i, Ybo.sFesCoSbn _. of Comparative Examples 4, 5 and 6 having the composition of gSno.i As a result of the analysis, the diffraction pattern was in good agreement with the Scudrudite reference data of the International Center for Diffraction Data (ICDD).

2. Temperature dependence of electrical conductivity

 The electrical conductivity of the P-type scuterudite thermoelectric material specimens prepared in Examples and Comparative Examples was measured according to temperature change, and is shown in FIG. 2, and the average values of 100 to 500 ° C. are shown in Table 1.

The decrease in the electrical conductivity of the P-type scudrudite thermoelectric materials of Examples and Comparative Examples with increasing temperature indicates that the synthesized scudrudite is a degenerate semiconductor. In addition, the electrical conductivity varies according to the oxidation value (oxidation state, Yb ⁺² , Nd ⁺² ~ ⁺³ , Ce + ³ + ⁺⁴ ) of the raw material used as the filler (M). When used at the same molar ratio (x = 0.8), the combination of fillers with lower oxidation rate increases the concentration of holes, which are P-type charge carriers, because fewer electrons are supplied to the scudrudite structure. High conductivity As shown in FIG. 2, the comparative example 6 in which only Yb is used as the filler shows the highest electrical conductivity and decreases in the order of (Ndjb), (Cejb), Nd, (Nd.Ce), and Ce. On the other hand, Examples 1, 2, and 3 have reduced electrical conductivity, respectively, compared to Comparative Examples 1, 2, and 3, in which Sn is not doped in place of Sb, which causes Sb to be replaced by Sn, causing point defect scattering, thereby preventing hole movement. It can be inferred as one.

3. Measurement of Seebeck Coefficient and Temperature Dependence of Seebeck Coefficient

The Seebeck coefficient _S was measured according to the temperature change of the P-type scuderudite thermoelectric material specimens prepared in Examples and Comparative Examples, and is shown in FIG. 3, and an average value of 100 to 500 ° C. is shown in Table 1. It was.

As shown in Figure 3, all the specimens can be evaluated as showing the conductivity of the p-type because it showed a positive Seebeck coefficient (+). In addition, in Examples 1, 2, and 3 in which two kinds of fillers were used and Sn was doped in Sb, Comparative Examples 1, 2, 3 and one in which Sb was not doped in Sb were used. Compared with the used Comparative Examples 4, 5, 6 it can be seen that the Seebeck coefficient further increased with increasing temperature.

4. Temperature dependence on output factors

The output factor of the P-type scuterudite thermoelectric material specimens prepared in Examples and Comparative Examples was calculated according to the temperature change, and is shown in FIG. 4, and an average value of 100 to 500 ^° C. is shown in Table 1.

Output factor was calculated using the value of the Power factor is defined as a = oS ^2, σ (electrical conductivity) shown in Figs. 2 and 3, and S (jebaek coefficient).

As shown in Fig. 4, as the temperature increases, the output factor increases and saturates, and then decreases again, and the SC of the Examples 1, 2, and 3 doped with Sn using two kinds of layered materials. In the case of a die, the output factor value is more superior to Comparative Examples 1, 2, 3, and Sn-doped Comparative Examples 4, 5, and 6, and particularly, Ndo.4Ybo.4Fe3CoSbn of Example 2. .9Sno.! In this case, the output factor measured at 400 ^° C. was very high, about 26 yW / crnK ² .

5. Temperature dependence of thermal conductivity

The thermal conductivity of the P-type scudrudite thermoelectric material specimens prepared in Examples and Comparative Examples was measured according to temperature change, and is shown in FIGS. 5 and 6. The total thermal conductivity (κ = KL + κ _Ε ) is divided into lattice thermal conductivity (K _l ) and thermal conductivity (κ _Ε ) calculated according to the Wiedemann-Franz law ( _KE = oLT), where Lorentz number (L) is the temperature The value calculated from the Seebeck coefficient according to was used. The total thermal conductivity κ is shown in FIG. 5, the average value of 100 to 500 ^° C. is shown in Table 1, and the lattice thermal conductivity (1) is shown in FIG. 6.

As shown in FIG. 5, the scutterrudites of Examples 1, 2 and 3, which used two fillers and were doped with Sn, were Comparative Examples 1, 2, 3, and one that were not doped with Sn. Thermal conductivity was further decreased compared to Comparative Examples 4, 5 and 6 using In addition, as shown in FIG. 6, in the case of the SC of the doped Sn 1, 2, 3, the lattice thermal conductivity was lower than that of Comparative Examples 1, 2, 3, This is because it acts as a phonon scattering center. In particular, the Ndo. 4Ybo. 4Fe3CoSbn. 9Sno. ! In case of 50CTC, it was very low, about 0.76 W / mK.

6. Temperature dependence of the thermoelectric figure of merit (ZT)

The dimensionless thermoelectric performance index (ZT) of the P-type scutterrudite thermoelectric material specimens prepared in Examples and Comparative Examples was calculated according to temperature change, and the average values of 100 to 500 ^° C. It was sandwiched in 1.

Thermoelectric performance index is defined as ZT = S ² OT / K, obtained in the experimental example

Calculations were made using values of S (seebeck coefficient), σ (electric conductivity) ᅳ Τ (absolute temperature) and κ (total thermal conductivity).

 Referring to FIG. 7 and Table 1, as the temperature is increased, the value of ΖΤ increased, and in the case of the scuterudite of Examples 1, 2 and 3 Sn-doped using two kinds of layered materials and Sn-doped, Sn-doped Comparative Examples 1, 2, 3 and

It can be seen that the thermoelectric performance index (ZT) was higher than that of Comparative Examples 4, 5, and 6 using one type of layered material.

7. Comparison of lattice constants and average thermoelectric properties between 100 and 500 ° C

 The lattice constants and the values of the average thermoelectric properties of 100-500 ° C. are shown in Table 1 for the P-type scuderudite thermoelectric material specimens prepared in Examples and Comparative Examples.

Table 1

단위 (A) (S/cm) ( u V/K) ( uW/cmK²) (W/mK)

Unit (A) (S / cm) (u V / K) (uW / cmK ² ) (W / mK)

Example 1 9.1148 1091 141 21.6 2.04 0.62 Comparative Example 1 9.1137 1124 132 19.4 2.14 0.53 Example 2 9.1198 1283 134 22.9 2.17 0.62 Comparative Example 2 9.1182 1336 131 22.6 2.26 0.58 Example 3 9.1201 1126 138 21.3 2.26 0.56 Comparative Example 3 9.1191 1186 134 21.2 2.37 0.52 Comparative Example 4 9.1215 1067 137 19.9 2.28 0.51 Comparative Example 5 9.1103 1181 134 21.1 2.28 0.54 Comparative Example 6 9.1286 1603 117 22.0 2.82 0.46 As shown in Table 1 above, Example 1 multi-layered and Sn-doped In the case of 2, 3, the lattice constant increased compared to Comparative Examples 1, 2 and 3 in which Sn was not doped, indicating that Sn having a large size was well substituted at the Sb site. On the other hand, in the case of Comparative Examples 4, 5, and 6 in which Sn was doped and a single layered material was used, the lattice constants were increased in the order of Yb, Ce, and Nd having larger sizes. And, in the case of the scutterrudites of Examples 1, 2 and 3 using two fillers and simultaneously Sn-doped, Comparative Examples 1, 2 and 3 without Sn and single-layered Sn-doped comparison Compared to Examples 4, 5, and 6, the average output factor value at 100 to 500 ^° C is improved and the average thermal conductivity is reduced, and it can be confirmed that the thermal performance index (ZT) is improved.

Claims

Claims [Paragraph 1] A p-type scrutherite thermoelectric material represented by the following general formula (1):  [Formula 1] M _x Fe4-yCoySbi2-zH _z  In Chemical Formula 1,  M is at least two elements selected from the group consisting of Ce, La, Sm, Nd, Yb, In and Ba,  H is at least one element selected from the group consisting of Sn, Ge, Se and Te,  0 <χ <1,  0 <y <4  0 <z <12. [Claim 2]  The method of claim 1,  A p-type scuterudite thermoelectric material according to Formula 1, wherein y 0 <y <1.5. [Claim 3]  The method of claim 1,  Z in Chemical Formula 1 is 0 <z≤0.2. [Claim 4]  The method of claim 1,  M is a P-type sciderrudite thermoelectric material, characterized in that at least two elements selected from the group consisting of Nd, 'Ce and Yb [Claim 5] The method of claim 1,  P-type scusterudite thermoelectric material, characterized in that H is Sn or Te. [Claim 6]  The method of claim 1,  P-type scudrudite thermoelectric material represented by the formula (1) _{Nd 0 .4Ce 0 .4Fe3.0Co1.0Sbn.9Sn 0 .1,} Nd 0. ₄ Ybo. ₄ Fe ₃ . ₀ Coi.oSbn. gSn ₀ .1, Ceo.4Ybo.4Fe3.oC01.oSb11.9Sno. ! P-type scuterudite thermoelectric material, characterized in that selected from the group consisting of. [Claim 7]  Fe, Co and Sb raw materials, Ce, La, Sm, Nd, Yb, In and Ba and two or more raw materials selected from the group consisting of 1, selected from the group consisting of Sn, .Ge, Se and Te Melting a mixture comprising at least one raw material;  Engraving the molten mixture to form an ingot;  Annealing the ingot;  Grinding the ingot into powder; And  Sintering the powder; Method of manufacturing a P-type skaterudite thermoelectric material comprising a. [Claim 8]  The method of claim 7, The melting temperature is 950 to 1200 ^° C. Method for producing a p-type scuterudite thermoelectric material. [Claim 9] The method of claim 7, The annealing temperature is 400 to 800, the manufacturing method of the P-type scudrudite thermoelectric material. [Claim 10]  The method of claim 7, The sintering temperature is 500 to 700 ^° C. Method for producing a p-type scuterutite thermoelectric material. [Claim 11]  A thermoelectric element comprising the P-type scudrudite thermoelectric material according to any one of claims 1 to 6.