Thermoelectric composite material and method for preparing thermoelectric composite material

Abstract

The present invention relates to a thermoelectric composite material and a method for preparing a thermoelectric composite material. Specifically, the invention relates to a thermoelectric composite material in which graphene oxide attached with conductive metal nanoparticles is dispersed in a thermoelectric material and a method for preparing a thermoelectric composite powder comprising the steps of: growing conductive metal nanoparticles on the surface of graphene oxide (step 1); and introducing the graphene oxide attached with the conductive metal nanoparticles prepared in step 1 into a thermoelectric material precursor solution, followed by heat treatment (step 2).

Claims

1. A thermoelectric composite material comprising: a functionalized graphene oxide including conductive metal nanoparticles on a surface of the functionalized graphene oxide, the functionalized graphene oxide being dispersed in a thermoelectric material.

2. The thermoelectric composite material according to claim 1, wherein the metal of the conductive metal nanoparticles is one or more metals selected from the group consisting of silver, copper, gold, platinum, and nickel.

3. The thermoelectric composite material according to claim 1, wherein the thermoelectric material is one or more compounds selected from the group consisting of BiTe compounds, SbTe compounds, BiSbTe compounds, CoSb compounds, PdTe compounds, GeTb compounds, SiGe compounds, and SmCo compounds.

4. The thermoelectric composite material according to claim 1, wherein the graphene oxide including conductive metal nanoparticles on the surface of the graphene oxide is prepared by growing the conductive metal nanoparticles on the surface of the graphene oxide after a functionalization of the graphene oxide.

5. The thermoelectric composite material according to claim 1, wherein a dimensionless figure-of-merit (ZT) of the thermoelectric composite material is improved at least as much as 1.2 times 2.0 times by that of the thermoelectric material in a temperature range of 20200 C.

6. A method for preparing a thermoelectric composite powder comprising the following steps: growing conductive metal nanoparticles on a surface of a functionalized graphene oxide (step 1); and introducing the functionalized graphene oxide including the conductive metal nanoparticles on the surface of the functionalized graphene oxide prepared in step 1 into a thermoelectric material precursor solution, followed by a heat treatment (step 2), the functionalized graphene oxide being dispersed in the thermoelectric material.

7. The method for preparing the thermoelectric composite powder according to claim 6, wherein the metal of the conductive metal nanoparticles is one or more metals selected from the group consisting of silver, copper, gold, platinum, and nickel.

8. The method for preparing the thermoelectric composite powder according to claim 6, wherein the surface of the functionalized graphene oxide of step 1 is attached with a functional group by one or more methods selected from the group consisting of ultrasonic process, acid treatment, and chemical treatment.

9. The method for preparing the thermoelectric composite powder according to claim 6, wherein the growing of the conductive metal nanoparticles in step 1 is achieved by heat-treating a conductive metal nanoparticle precursor at 50 150 C. in a basic solution (pH 8 10).

10. The method for preparing the thermoelectric composite powder according to claim 6, wherein the thermoelectric material precursor solution of step 2 contains one or more thermoelectric material precursors selected from a group consisting of bismuth acetate, bismuth chloride, bismuth nitrate, tellurium chloride, selenium chloride, and antimony chloride.

11. The method for preparing the thermoelectric composite powder according to claim 6, wherein the thermoelectric material precursor solution of step 2 contains a surfactant and a reducing solvent.

12. The method for preparing the thermoelectric composite powder according to claim 11, wherein the surfactant is one or more materials selected from the group consisting of oleylamine (OLA), trioctylphosphine (TOP), and oleic acid.

13. The method for preparing the thermoelectric composite powder according to claim 11, wherein the reducing solvent is l-dodecanethiol.

14. The method for preparing the thermoelectric composite powder according to claim 6, wherein the functionalized graphene oxide including the conductive metal nanoparticles on the surface of the functionalized graphene oxide of step 2 is introduced in the thermoelectric material precursor solution at a concentration of 0.02 weight% 5 weight% of the solution.

15. The method for preparing the thermoelectric composite powder according to claim 6, wherein the heat treatment in step 2 is performed at 90 250 C. for 13 hours.

16. A method for preparing a thermoelectric composite powder comprising the following steps: growing conductive metal nanoparticles on a surface of a functionalized graphene oxide (step 1); and mixing mechanically the functionalized graphene oxide including the conductive metal nanoparticles on the surface of the functionalized graphene oxide prepared in step 1 with a thermoelectric material powder (step 2), the functionalized graphene oxide being dispersed in the thermoelectric material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The application of the preferred embodiments of the present invention is best understood with reference to the accompanying drawings, wherein:

(2) FIG. 1 is a schematic diagram illustrating the structure of the thermoelectric composite material of the present invention;

(3) FIG. 2 is a flow chart illustrating an example of the method for preparing the thermoelectric composite powder of the present invention;

(4) FIG. 3 is a SEM photograph illustrating the graphene oxide attached with silver nanoparticles prepared in step 2 of Example 1;

(5) FIG. 4 is a SEM photograph illustrating the microstructure of the thermoelectric composite powder prepared in step 3 of Example 1;

(6) FIG. 5 is a SEM photograph illustrating the microstructure of the thermoelectric composite material prepared in step 4 of Example 1;

(7) FIG. 6 is a graph illustrating the composition of the thermoelectric composite material prepared in step 4 of Example 1, observed with X-ray diffractometer;

(8) FIG. 7 is a graph illustrating the electrical resistivity of the thermoelectric materials prepared in Example 1 and Comparative Examples 1 and 2;

(9) FIG. 8 is a graph illustrating the thermal conductivity of the thermoelectric materials prepared in Example 1 and Comparative Examples 1 and 2;

(10) FIG. 9 is a graph illustrating the dimensionless figure-of-merit (ZT) of the thermoelectric materials prepared in Example 1 and Comparative Examples 1 and 2;

(11) FIG. 10 is a SEM photograph illustrating the microstructure of the thermoelectric composite material prepared in Example 2;

(12) FIG. 11 is a graph illustrating the composition of the thermoelectric composite material prepared in Example 2, observed with X-ray diffractometer;

(13) FIGS. 1215 are graphs illustrating the electrical conductivity, Seebeck coefficient, power factor, and thermal conductivity of the thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4;

(14) FIG. 16 is a graph illustrating the lattice thermal conductivity of the thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4;

(15) FIG. 17 is a graph illustrating the charge thermal conductivity of the thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4;

(16) FIG. 18 is a graph illustrating the Seebeck coefficient plotted for the carrier concentration of the thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4;

(17) FIG. 19 is a graph illustrating the dimensionless figure-of-merit (ZT) of the thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

(18) Hereinafter, the present invention is described in detail.

(19) The present invention provides a thermoelectric composite material in which graphene oxides attached with conductive metal nanoparticles are dispersed in a thermoelectric material.

(20) A schematic diagram illustrating the thermoelectric composite material of the present invention is presented in FIG. 1.

(21) Hereinafter, the thermoelectric composite material of the invention is described in more detail.

(22) According to the previous art, in order to increase the electrical conductivity but to decrease the thermal conductivity of a thermoelectric material, the nano-sized oxide particles such as ZrO.sub.2 and Al.sub.2O.sub.3 or the nano-sized dispersion agents having 1-dimensional structure were added to a thermoelectric material to induce phonon scattering effect in the thermoelectric material and thereby to reduce the thermal conductivity. However, the electrical conductivity was also reduced and eventually it was difficult to increase the thermoelectric figure-of-merit. As an alternative conductive nano-sized dispersion agent, carbon nanotube has been proposed. However, in order to disperse the carbon nanotube, the surface has to be treated with a strong acid and this functionalization can cause the decrease of the electrical conductivity.

(23) To solve the said problem, graphene oxide in a 2-dimensional structure is used in this invention as a dispersion agent. A material comprising the 2-dimensional graphene oxide/conductive metal nanoparticles can form new interfaces on both sides, unlike the conventional carbon nanotube in a 1-dimensional linear structure can form a new interface only on the outer side. So, the phonon scattering effect at the newly formed interface and the surface can be synergistically maximized. In this invention, after the functionalization of the graphene oxide, conductive nanoparticles are attached so that the defect of the graphene oxide can be prevented and the deterioration of the electrical conductivity can also be prevented. That is, the oxygen-contained fuctional groups in the graphene oxide of the invention can successfully act as a seed on which a thermoelectric material can be attached.

(24) The thermoelectric composite material of the present invention is advantageous in realizing two different thermal and electric characteristics because it can minimize the thermal conductivity by reducing phonon transfer significantly by using the graphene oxide having the 2-dimensional structure but can maintain or even improve carrier transfer by the attached conductive metal nanoparticles. In this invention, the concept that can minimize heat transfer with maintaining electric properties is defined as thermal metamaterials.

(25) At this time, the metal included in the conductive metal nanoparticle can be one of the metals selected from the group consisting of silver, copper, gold, platinum, and nickel, but not always limited thereto and any metal that can endow an excellent electrical conductivity to a thermoelectric composite material can be used.

(26) The thermoelectric material herein is selected from the group consisting of BiTe compounds, SbTe compounds, BiSbTe compounds, CoSb compounds, PbTe compounds, GeTb compounds, SiGe compounds, and SmCo compounds, but not always limited thereto. Among them, BiTe compounds are preferred.

(27) In the meantime, in the graphene oxide attached with the conductive metal nanoparticles, the conductive metal nanoparticles are growing on the surface of graphene oxide after the functionalization of the graphene oxide. By the completion of the functionalization, the graphene oxide can be homogeneously dispersed in a thermoelectric matrix material and thereby the reduced electrical conductivity caused by the functionalization can be compensated or improved by the attached conductive metal nanoparticles.

(28) The thermoelectric composite material of the invention is characterized by a high dimensionless figure-of-merit (ZT) which is improved as high as 1.22.0 times by that of the matrix material in the temperature range of 20200 C. Such a high dimensionless figure-of-merit resulted from the low thermal conductivity but the improved electrical conductivity of the thermoelectric composite material of the invention is realized by the scattering of the graphene oxide attached with conductive metal nanoparticles.

(29) The present invention also provides a method for preparing a thermoelectric composite powder comprising the following steps:

(30) growing conductive metal nanoparticles on the surface of graphene oxide (step 1); and

(31) introducing the graphene oxide attached with the conductive metal nanoparticles prepared in step 1 into a thermoelectric material precursor solution, followed by heat treatment (step 2).

(32) A schematic diagram illustrating the method for preparing a thermoelectric composite powder of the present invention is presented in FIG. 2.

(33) Hereinafter, the method for preparing a thermoelectric composite powder of the present invention is described in more detail step by step.

(34) In the method for preparing a thermoelectric composite powder of the present invention, step 1 is to grow conductive metal nanoparticles on the surface of graphene oxide. In step 1, the electrical conductivity of the thermoelectric composite powder containing the graphene oxide can be improved by growing the conductive metal nanoparticles on the surface of the graphene oxide.

(35) At this time, the metal included in the conductive metal nanoparticle of step 1 can be one of the metals selected from the group consisting of silver, copper, gold, platinum, and nickel, but not always limited thereto and any metal that can endow an excellent electrical conductivity to a thermoelectric composite material can be used.

(36) In the meantime, the surface of the graphene oxide of step 1 can be treated by one or more methods selected from the group consisting of ultrasonic process, acid treatment, and chemical treatment in order to attach a functional group thereto, but not always limited thereto. By the attachment of a functional group via one of the said methods, the graphene oxide can be better dispersed in a thermoelectric matrix material.

(37) The growing of the conductive metal nanoparticles in step 1 can be achieved by heat-treating the conductive metal nanoparticle precursor at 50150 C. in a basic solution (pH 810), but the growing process of the metal nanoparticles is not limited thereto.

(38) In the method for preparing a thermoelectric composite powder of the present invention, step 2 is to introduce the graphene oxide attached with the conductive metal nanoparticles prepared in step 1 into a thermoelectric material precursor solution, followed by heat-treatment. In step 2, the graphene oxide attached with the conductive nanoparticles is dispersed in the thermoelectric material to prepare the thermoelectric composite powder.

(39) At this time, the thermoelectric material precursor solution of step 2 can contain one or more thermoelectric material precursors selected from the group consisting of bismuth acetate, bismuth chloride, bismuth nitrate, tellurium chloride, selenium chloride, and antimony chloride, but not always limited thereto.

(40) In the meantime, the thermoelectric material precursor solution of step 2 can contain a surfactant and a reducing solvent, and at this time, the surfactant can be selected from the group consisting of oleylamine (OLA), trioctylphosphine (TOP), and oleic acid. The reducing solvent can be 1-dodecanethiol, but the surfactant and the reducing solvent above are not limited thereto.

(41) The graphene oxide attached with the conductive metal nanoparticles of step 2 can be introduced in the thermoelectric material precursor solution at the concentration of 0.025 weight % by the weight of the precursor solution.

(42) If the concentration of the graphene oxide included in the thermoelectric material precursor solution is less than 0.02 weight %, the phonon scattering effect would be very weak, and if the concentration of the grapheme oxide is more than 5 weight %, coagulation is caused due to the excessive oxide material.

(43) The heat-treatment in step 2 is preferably performed at 90250 C. for 13 hours.

(44) If the heat-treatment in step 2 is performed out of the temperature range above, the reduction of the thermoelectric material cannot be controlled. If the heat-treatment in step 2 is performed for less than an hour, the reduction would not be completed, indicating that the atoms of the thermoelectric material cannot be reduced and accordingly the yield of the thermoelectric material would be decreased. If the heat-treatment continues for more than 3 hours, it would be waste of time and costs.

(45) The present invention also provides a method for preparing a thermoelectric composite powder comprising the following steps:

(46) growing conductive metal nanoparticles on the surface of graphene oxide (step 1); and

(47) mixing mechanically the graphene oxide attached with the conductive metal nanoparticles prepared in step 1 with the thermoelectric material powder (step 2).

(48) Hereinafter, the method for preparing a thermoelectric composite powder of the present invention is described in more detail step by step.

(49) In the method for preparing a thermoelectric composite powder of the present invention, step 1 is to grow conductive metal nanoparticles on the surface of graphene oxide. In step 1, the electrical conductivity of the thermoelectric composite powder containing the graphene oxide can be improved by growing the conductive metal nanoparticles on the surface of the graphene oxide.

(50) The step 1 above can be performed by the same manner as described above, so the details are not repeated herein.

(51) In the method for preparing a thermoelectric composite powder of the present invention, step 2 is to mix mechanically the graphene oxide attached with the conductive metal nanoparticles prepared in step 1 with the thermoelectric material powder. By this mechanical mixing, the graphene oxide can be dispersed in the thermoelectric material.

(52) The graphene oxide attached with the conductive metal nanoparticles of step 2 can be introduced in the thermoelectric material powder at the concentration of 0.025 weight % by the weight of the thermoelectric material powder.

(53) If the concentration of the graphene oxide included in the thermoelectric material precursor solution is less than 0.02 weight %, the phonon scattering effect would be very weak, and if the concentration of the grapheme oxide is more than 5 weight %, coagulation is caused due to the excessive oxide material.

(54) In step 2, the mixture of the graphene oxide attached with the conductive metal nanoparticles and the thermoelectric material powder can additionally contain graphene oxide.

(55) At t his time, the graphene oxide can be introduced at the concentration of 0.025 weight % by the weight of the thermoelectric material powder.

(56) Further, the mechanical mixing in step 2 can be performed by planetary milling process at 250 rpm 1,000 rpm for 110 hours.

(57) The present invention also provides a thermoelectric composite powder prepared by the method of the invention above and characteristically containing graphene oxide attached with conductive metal nanoparticles in the thermoelectric material powder.

(58) The thermoelectric composite powder prepared by the method of the invention displays a lower thermal conductivity due to the decrease of phonon scattering caused by the graphene oxide attached with conductive metal nanoparticles which is dispersed in a thermoelectric material powder but an improved electrical conductivity due to the conductive metal nanoparticles included therein.

(59) The present invention also provides a method for preparing a thermoelectric composite material comprising the step of pressure-assisted sintering the thermoelectric composite powder prepared by the method of the invention above at 250400 C. with the pressure of 3070 MPa.

(60) The pressure-assisted sintering process above makes the bulking of a thermoelectric composite material that is not suitable for the general sintering to give the bulked thermoelectric composite material.

(61) If the sintering of the thermoelectric composite powder is performed at a temperature less than 250 C., it is difficult to prepare a sintered body with a sufficient density. If the sintering is performed at a temperature higher than 400 C., a sample could be damaged due to a high temperature and costs are wasted.

(62) If the sintering is performed at a pressure less than 30 PMa, it is difficult to prepare a sintered body with a sufficient density and the final sample would have too weak strength to be used. If the sintering is performed at a pressure higher than 70 MPa, it is a waste of costs.

(63) The pressure-assisted sintering can be performed by spark plasma sintering process for 130 minutes or by hot press process for 12 hours, but not always limited thereto.

(64) The present invention also provides a thermoelectric composite material prepared by the method above.

(65) The present invention also provides a thermoelectric composite material characteristically prepared by the method of the invention above, wherein the electrical resistivity is 0.62.510.sup.5 /m, the thermal conductivity is 0.61.2 W/mK, and the dimensionless figure-of-merit (ZT) is 0.42.0 at 20200 C.

(66) The thermoelectric composite material prepared by the method of the invention above displays a lower thermal conductivity due to the decrease of phonon scattering caused by the graphene oxide attached with conductive metal nanoparticles which is dispersed in a thermoelectric material powder but an improved electrical conductivity due to the conductive metal nanoparticles included therein. As a result, the composite material can have a high dimensionless figure-of-merit.

(67) The present invention also provides a thermoelectric material comprising the thermoelectric composite material above for the electricity generation using waste-heat at room temperature under 450K.

(68) The present invention also provides a thermoelectric material comprising the thermoelectric composite material above for the precise cooling and heating at room temperature under 450K.

(69) The thermoelectric composite material of the present invention has a high dimensionless figure-of-merit, so that it can be used not only as a low temperature waste-heat conversion material under 450K but also as a thermoelectric material for the precise cooling and heating in the course of power supply. However, the use of the thermoelectric composite material is not limited to the above, and further the thermoelectric material can be applied as a special power supply unit for the thermoelectric generation for remote mountainous regions, for space industry, and for military purpose; and also used for the precise temperature control by using thermoelectric refrigeration in semiconductor laser diode and infrared sensing element, for the computer related small cooling system and the optical communication laser cooling system, for the chiller-heater cooling system, for the semiconductor temperature control system, for the heat exchanger, for the small refrigerator, for the cooling/heating control system of a car seat, etc.

(70) Practical and presently preferred embodiments of the present invention are illustrative as shown in the following Examples.

(71) However, it will be appreciated that those skilled in the art, on consideration of this disclosure, may make modifications and improvements within the spirit and scope of the present invention.

Example 1: Preparation of GO/Ag/BiSbTe Thermoelectric Composite Material 1

(72) Step 1: 1 g of highly oriented polycrystalline graphite was added to sulfuric acid solution, and the mixture was stirred with ultrasonic irradiation for 10 minutes. In the course of the process, the graphite was separated as a thin graphene layer.

(73) Then, 3.5 g of KMnO.sub.4 was slowly added to the solution above for 1015 minutes with stirring in an ice bath. The mixture was stirred mechanically at 35 C. for 2 hours. 510 mL of hydrogen peroxide was added to the mixture above, which was stirred until the color changed from green to brown. The final solution was filtered with a glass filter and washed with 10% HCl solution. The obtained powder was dried to give a graphene oxide. During the HCl treatment, a carboxyl group (COOH) or a carbonyl group (CO) containing oxygen was adhered to the surface to prepare a graphene oxide having a functional group attached thereto.

(74) Step 2: 0.003 g of Ag(NO.sub.3) was added to the solution wherein the graphene oxide prepared in step 2 was dispersed at the concentration of 2 mg/ml, and then NH.sub.3OH solution was added thereto to regulate pH of the solution as 1012. Then, 1.1 ml of hydrazine (N.sub.2H.sub.2) solution was added thereto, followed by heating until the temperature reached 95 C. As a result, GO/Ag material containing a graphene oxide on which conductive nanoparticles were grown was prepared, which was dispersed in distilled water.

(75) Step 3: bismuth acetate (Bi(CH.sub.3COO).sub.3), tellurium chloride (TeCl.sub.4), and antimony chloride (SbCl.sub.3) were added as thermoelectric material precursors at the concentrations of 0.153 g, 0.162 g, and 0.288 g respectively, to which 9 ml of oleylamine was added as a surfactant, and 100 ml of 1-dodecanethiol was added as a reducing solvent, resulting in the preparation of a thermoelectric precursor solution. The GO/Ag material prepared in step 2 was added to the thermoelectric material precursor solution at the concentration of 1 weight % (0.001 g). The solution was heat-treated at 200 C. for 2 hours and as a result, GO/Ag/BiSbTe thermoelectric composite powder was prepared.

(76) Step 4: Pressure-assisted sintering of the thermoelectric composite powder prepared in step 3 was performed by spark plasma sintering process at 350 C. for 10 minutes with the pressure of 70 MPa. As a result, bulk type GO/Ag/BiSbTe thermoelectric composite material was prepared.

Example 2: Preparation of GO/Ag/BiSbTe Thermoelectric Composite Material 2

(77) Step 1: 1 g of highly oriented polycrystalline graphite was added to sulfuric acid solution, and the mixture was stirred with ultrasonic irradiation for 10 minutes. In the course of the process, the graphite was separated as a thin graphene layer.

(78) Then, 3.5 g of KMnO.sub.4 was slowly added to the solution above for 1015 minutes with stirring in an ice bath. The mixture was stirred mechanically at 35 C. for 2 hours. 510 mL of hydrogen peroxide was added to the mixture above, which was stirred until the color changed from green to brown. The final solution was filtered with a glass filter and washed with 10% HCl solution. The obtained powder was dried to give a graphene oxide. During the HCl treatment, a carboxyl group (COOH) or a carbonyl group (CO) containing oxygen was adhered to the surface to prepare a graphene oxide having a functional group attached thereto.

(79) Step 2: 0.003 g of Ag(NO.sub.3) was added to the solution wherein the graphene oxide prepared in step 2 was dispersed at the concentration of 2 mg/ml, and then NH.sub.3OH solution was added thereto to regulate pH of the solution as 1012. Then, 1.1 ml of hydrazine (N.sub.2H.sub.2) solution was added thereto, followed by heating until the temperature reached 95 C. As a result, GO/Ag material containing a graphene oxide on which conductive nanoparticles were grown was prepared, which was dispersed in distilled water.

(80) Step 3: The thermoelectric material powder having the composition of Bi.sub.0.5Sb.sub.1.5Te.sub.3 was prepared via mechanical ball milling process, in which the atomic ratio of Bi:SB:TE was 0.5:1.5:3.0. The thermoelectric material powder above was mixed with the GO/Ag material prepared in step 2 (0.1 weight %) and the graphene oxide powder (0.1 weight %) by high energy milling process at 450 rpm for 26 hours. As a result, GO/Ag/BiSbTe thermoelectric composite powder was prepared.

(81) Step 4: Pressure-sintering of the thermoelectric composite powder prepared in step 3 was performed by spark plasma sintering process at 350 C. for 10 minutes with the pressure of 3070 MPa. As a result, bulk type GO/Ag/BiSbTe thermoelectric composite material was prepared.

Comparative Example 1: Preparation of BiSbTe Thermoelectric Material 1

(82) BiSbTe thermoelectric material was prepared by the same manner as described in Example 1 except that the GO/Ag material prepared in step 1 and step 2 of Example was not included.

Comparative Example 2: Preparation of GO/BiSbTe Thermoelectric Composite Material 1

(83) GO/BiSbTe thermoelectric composite material was prepared by the same manner as described in Example 1 except that step 2 of Example 1 was not performed and the graphene oxide prepared in step 1 was added in step 3.

Comparative Example 3: Preparation of BiSbTe Thermoelectric Material 1

(84) BiSbTe thermoelectric material was prepared by the same manner as described in Example 2 except that the GO/Ag material prepared in step 1 and step 2 of Example 2 was not included.

Comparative Example 4: Preparation of GO/BiSbTe Thermoelectric Composite Material 2

(85) GO/BiSbTe thermoelectric composite material was prepared by the same manner as described in Example 2 except that step 2 of Example 2 was not performed and the graphene oxide prepared in step 1 was added in step 3.

Experimental Example 1: Observation of Microstructure and Composition of Thermoelectric Composite Material 1

(86) The microstructure of the thermoelectric material prepared in Example 1 was observed under scanning electron microscope (SEM), and the results are shown in FIG. 3FIG. 5. The phase of the thermoelectric material prepared in Example 1 was observed with X-ray diffractometer and the results are shown in FIG. 6.

(87) As shown in FIG. 3, silver nanoparticles are attached regularly on the surface of the graphene oxide in the GO/Ag material prepared in step 2.

(88) As shown in FIG. 4, the graphene oxide attached with silver nanoparticles is dispersed in BiSbTe powder in the GO/Ag/BiSbTe thermoelectric composite powder prepared in step 3.

(89) As shown in FIG. 5, the graphene oxide is dispersed in BiSbTe matrix in the Go/Ag/BiSbTe thermoelectric composite material prepared in step 4.

(90) As shown in FIG. 6, the composition of the thermoelectric composite material prepared by the method of the invention was Bi.sub.0.5Sb.sub.1.5Te.sub.3, indicating that the composite material having the base composition of BiSbTe was successfully prepared.

Experimental Example 2: Observation of Thermoelectric Properties of Thermoelectric Composite Material 1

(91) To observe the thermoelectric properties of the thermoelectric materials prepared in Example 1 and Comparative Examples 1 and 2, the electrical resistivity was measured by using Ulvac-Rico Zem-3 and the results are shown in FIG. 7. The thermal conductivity was investigated by Laser flash method using LFA-447 (Netzsch) and converted by using the density and specific heat of each sample. The results are shown in FIG. 8. The dimensionless figure-of-merit was calculated by using all the measured electrical resistivity, Seebeck coefficient, and thermal conductivity above and the results are shown in FIG. 9.

(92) As shown in FIG. 7, the electrical resistivity of the materials of Comparative Examples 1 and 2 was approximately 2410.sup.5 /m, which was two times as high as that of the material of Example 1 (1210.sup.5 /m).

(93) As shown in FIG. 8, the thermal conductivity of the materials of Comparative Example 2 and Example 1 was 0.750.9 W/mK and the thermal conductivity of the material of Comparative Example 1 was 0.951.1 W/mK, indicating that the material of Comparative Example 1 which did not contain graphene oxide displayed higher thermal conductivity than the materials of Comparative Example 2 and Example 1 containing graphene oxide. Therefore, it was confirmed that the addition of graphene oxide could reduce the thermal conductivity by increasing phonon scattering.

(94) As shown in FIG. 9, ZT of the material of Comparative Example was 0.250.6 at the temperature of 20200 C. ZT of the material of Comparative Example 2 was 0.250.8 and ZT of the material of Example 1 was 0.41.2.

(95) From the above results, it was confirmed that the material of Comparative Example 1 that did not contain graphene oxide had a higher thermal conductivity and resistivity. The material of Comparative Example 2 that did contain graphene oxide but did not contain metal nanoparticles attached thereto displayed a low thermal conductivity and electrical conductivity.

(96) The thermoelectric material of Example 1 containing graphene oxide attached with metal nanoparticles displayed a high electrical conductivity but a low thermal conductivity, indicating that it showed excellent ZT.

(97) The above results were obtained by the present invention under such conditions described above, and it is expected to obtain a more improved ZT by decreasing the size of the powder prepared according to the present invention or to regulate the content of the graphene oxide or by regulating the size, the amount, and the kinds of metal nanoparticles.

Experimental Example 3: Observation of Microstructure and Composition of Thermoelectric Composite Material 2

(98) The microstructure of the thermoelectric material prepared in Example 2 was observed under scanning electron microscope (SEM), and the results are shown in FIG. 10. The phase of the thermoelectric material prepared in Example 2 was observed with X-ray diffractometer and the results are shown in FIG. 11.

(99) As shown in FIG. 10, it was confirmed that GO/Ag/BiSbTe thermoelectric composite material was produced by mechanical mixing as a powder form.

(100) As shown in FIG. 11, the composition of the thermoelectric composite material prepared according to the method of the invention was Bi.sub.0.5Sb.sub.1.5Te.sub.3 which was the composition of the BiSbTe matrix material.

Experimental Example 4: Characterization of Thermoelectric Properties of Thermoelectric Composite Material 2

(101) To characterize the thermoelectric properties of those thermoelectric materials prepared in Example 2 and Comparative Examples 3 and 4, the electrical conductivity (), Seebeck coefficient (S), power factor, and thermal conductivity () were measured and the results are shown in FIG. 12FIG. 15. The lattice thermal conductivity (.sub.lat) and charge thermal conductivity (.sub.el) were also calculated and the results are shown in FIG. 16 and FIG. 17. The carrier concentration (n) dependent Seebeck coefficient was plotted and the results are shown in FIG. 18. The dimensionless figure-of-merit (ZT) was calculated by using all the measured electrical conductivity, Seebeck coefficient, and thermal conductivity above and the results are shown in FIG. 19.

(102) As shown in FIGS. 1215, the electrical conductivity of the thermoelectric material of Comparative Example 3 was approximately 3.710.sup.4 S/m5.110.sup.4 S/m. The electrical conductivity of the thermoelectric material of Comparative Example 4 was approximately 3.710.sup.4 S/m5.710.sup.4 S/m. In the meantime, the electrical conductivity of the thermoelectric material of Example 2 was approximately was as low as approximately 3.710.sup.4 S/m4.710.sup.4 S/m.

(103) Therefore, it was confirmed that the material of Example 2 had a lower thermal conductivity than those materials of Comparative Examples 3 and 4.

(104) Further, the Seebeck coefficient of the material of Example 2 of the invention was higher than that of those materials of Comparative Examples 3 and 4.

(105) As shown in FIG. 16 and FIG. 17, the material of Example 2 was confirmed to have a low thermal conductivity, supported by the results of .sub.lat and .sub.el. That is, although three examples shows similar .sub.el values, GO/Ag/BiSbTe thermoelectric composite material displays the lowest .sub.lat value among them. the phonon scattering was actively occurred in the GO/Ag/BiSbTe material.

(106) As shown in FIG. 18, the Seebeck coefficient of the GO/Ag/BiSbTe thermoelectric composite material of Example 2 was increased. That was understood because of the relative increase of effective mass (m*) in the following mathematical formula 1.

(107) $\begin{array}{cc}=\frac{8{}^2{k}_b^2}{3{\mathrm{eh}}^2}{m}^{*}{T\left(\frac{}{3n}\right)}^{2/3}& .Math.\mathrm{Mathematical}\mathrm{Formula}1.Math.\end{array}$

(108) As shown in FIG. 19, the maximum ZT of the thermoelectric composite material of the present invention prepared in Example 2 was as excellent as about 1.7 at 350 K.

(109) The above results were obtained by the present invention under such conditions described above, and it is expected to obtain a more improved ZT by reducing the size of the powder prepared according to the present invention or to regulate the content of the graphene oxide or by regulating the size, the amount, and the kinds of metal nanoparticles.

(110) Those skilled in the art will appreciate that the conceptions and specific embodiments disclosed in the foregoing description may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present invention. Those skilled in the art will also appreciate that such equivalent embodiments do not depart from the spirit and scope of the invention as set forth in the appended Claims.