Patent Grant
11276809
This application claims the benefit of Korean Patent Application No. 10-2016-0142891 filed on Oct. 31, 2016 and Korean Patent Application No. 10-2017-0134204 filed on Oct. 16, 2017 with the Korean Intellectual Property Office, the disclosure of which is herein incorporated by reference in its entirety.
The present invention relates to a novel chalcogen-containing compound that exhibits low thermal conductivity and excellent thermoelectric properties, and exhibits excellent phase stability even at relatively low temperature, a method for preparing the same, and a thermoelectric element including the same.
Due to recent environmental problems caused by resource depletion and combustion, studies on thermoelectric conversion materials using waste heat are progressing as one of alternative energy sources.
The energy conversion efficiency of such thermoelectric conversion material depends on a thermoelectric figure of merit (ZT). Here, ZT is determined according to the Seebeck coefficient, electrical conductivity, thermal conductivity, etc., and more specifically, it is proportional to the square of the Seebeck coefficient and electrical conductivity, and is inversely proportional to thermal conductivity. Thus, in order to increase the energy conversion efficiency of a thermoelectric element, the development of a thermoelectric conversion material having a high Seebeck coefficient or electrical conductivity or low thermal conductivity is required.
Among the various thermoelectric conversion materials known before, thermoelectric conversion materials with a crystal lattice structure related to or similar to sodium chloride (NaCl), in which a part of the lattice site is vacant, such as PbTe, Bi2Te3, SnSe, etc., for example, are known to exhibit an excellent thermoelectric conversion property. That is, it is considered that materials having such a crystal lattice structure exhibit excellent electrical conductivity due to the crystal lattice structure similar to sodium chloride, and exhibit low thermal conductivity because a part of the lattice site becomes vacant. Thus, thermoelectric conversion materials having the above-described crystal lattice structure are known to have an excellent thermoelectric conversion property, and thus are being applied.
Nevertheless, little is known about a thermoelectric conversion material that has face-centered cubic lattice structure identical to sodium chloride as shown in
However, Sn4Bi2Se7, one of Si—Bi—Se-based chalcogen compounds, is known to have an identical face-centered cubic lattice structure to that of sodium chloride, and includes a lattice site of which a part is vacant. For reference,
However, such chalcogen compounds maintain stability only at a temperature range of about 580 to 720° C., and at lower temperature, particularly at the driving temperature of a thermoelectric element, they cannot exhibit phase stability because they are decomposed to other phases.
Consequently, although it is expected that the above-described chalcogen compound exhibits low thermal conductivity and an excellent thermoelectric property because it has a face-centered cubic lattice structure including a lattice site of which a part is vacant, it exhibits inferior phase stability at a low temperature of about 580° C. or less, corresponding to the general driving temperature of thermoelectric elements, and thus application as a thermoelectric conversion material is very limited.
The present invention provides a novel chalcogen-containing compound that exhibits low thermal conductivity and excellent thermoelectric properties, and exhibits excellent phase stability even at relatively low temperature, and a method for preparing the same.
Further, the present invention provides a thermoelectric element including the chalcogen-containing compound.
The present invention provides a chalcogen-containing compound represented by the following Chemical Formula 1:
MxSnyBizSe7 [Chemical Formula 1]
wherein, in Chemical Formula 1, M is an alkali metal,
x, y and z are mole ratios of M, Sn, and Bi respectively, x is greater than 0 and equal to or less than 2, y is greater than 0 and equal to or less than 4, z is greater than 0 and equal to or less than 2, y+z is greater than 0 and equal to or less than 6, and x+y+z is greater than 0 and equal to or less than 7.
The present invention also provides a method for preparing the chalcogen-containing compound, comprising the steps of:
progressing a solid phase reaction of a mixture comprising raw materials comprising Sn, Bi and Se, and raw material comprising alkali metal (M),
grinding the product of the solid phase reaction; and
sintering the ground product.
The present invention also provides a thermoelectric element comprising the chalcogen-containing compound as a thermoelectric conversion material.
Hereinafter, a chalcogen-containing compound, a method for preparing the same, and a thermoelectric element including the same according to specific embodiments of the invention will be explained in detail.
According to one embodiment of the present invention, a chalcogen-containing compound represented by the following Chemical Formula 1 is provided.
MxSnyBizSe7 [Chemical Formula 1]
wherein, in Chemical Formula 1, M is an alkali metal,
x, y and z are mole ratios of M, Sn, and Bi respectively, x is greater than 0 and equal to or less than 2, y is greater than 0 and equal to or less than 4, z is greater than 0 and equal to or less than 2, y+z is greater than 0 and equal to or less than 6, and x+y+z is greater than 0 and equal to or less than 7.
The chalcogen-containing compound of the one embodiment is a compound represented by Chemical Formula 1 in which an alkali metal is added to a chalcogen compound such Sn4Bi2Se7, and it has the same crystal lattice structure as Sn4Bi2Se7, that is, a crystal structure of a face-centered cubic lattice structure that is identical to that of sodium chloride.
More specifically, in the compound of the one embodiment, it appears that a part of a vacancy excluding the sites filled with Se, Sn and Bi is filled with the alkali metal atom, in the face-centered cubic lattice structure. A vacancy remaining after filled with the alkali metal atom may be maintained as it is, and the value of 7−(x+y+z) may be defined as the mole ratio of the vacancy.
As demonstrated in the examples described below, it was confirmed that the compound of the one embodiment can exhibit excellent electrical conductivity due to the crystal lattice structure of a face-centered cubic lattice structure and the addition of an alkali metal. This results from the crystal lattice structure, and simultaneously, is because the alkali metal becomes in the form of ions, thus donating additional electrons.
Further, the compound of the one embodiment has the above-described specific crystal structure, but the alkali metal does not completely fill the vacant lattice site, and a part thereof remains, and thus, the compound has low thermal conductivity. Thus, the compound of the one embodiment exhibits excellent thermoelectric conversion property resulting from high electric conductivity and low thermal conductivity.
Moreover, it was confirmed that since the chalcogen-containing compound of the one embodiment has an alkali metal added in the crystal lattice structure, it exhibits excellent phase stability even at a low temperature (for example, a temperature of about 580° C. or more) corresponding to the driving temperature of a thermoelectric element. Such excellent phase stability can be confirmed by the maintenance of an identical XRD pattern and an identical crystal structure without decomposition of the compound, even when the chalcogen-containing compound of the one embodiment is finally prepared and left in the form of a sintered body, as shown in
Thus, the chalcogen-containing compound of one embodiment overcomes the problems of previously known Sn4Bi2Se7, etc. in terms of inferior phase stability, and exhibits excellent phase stability even at the general driving temperature of a thermoelectric element, and simultaneously, exhibits excellent electrical conductivity, low thermal conductivity and excellent thermoelectric conversion property due to the unique crystal lattice structure. Thus, the chalcogen-containing compound of one embodiment can be very preferably used as a thermoelectric conversion material in various fields and applications.
Meanwhile, as explained above, in the face-centered cubic lattice structure of the chalcogen-containing compound of one embodiment, at least a part of the vacancy excluding the sites filled with Se, Sn, and Bi is filled with the alkali metal atom. More specifically, in such a face-centered cubic lattice structure, the Se fills the anion sites of the face-centered cubic lattice structure, the Sn and Bi fill the cation sites of the face-centered cubic lattice structure, and the alkali metal (M) fills a part of a vacancy of the cation sites remaining after filled with Sn and Bi.
Herein, the alkali metal, and Sn and Bi that fill each cation site become cations, and can donate electrons, thus contributing to the excellent electrical conductivity of the compound of one embodiment. In addition, since the addition of the alkali metal may contribute to excellent phase stability, and the alkali metal cannot completely fill the vacant lattice site and a vacancy remains, the chalcogen-containing compound of one embodiment may exhibit low thermal conductivity.
As the alkali metal, one or more alkali metals selected from the group consisting of Na, and K may be used, but considering high electrical conductivity and excellent phase stability of the compound of one embodiment, Na may be appropriately used.
And, in the Chemical Formula 1, x, y and z denote mole ratios of M, Sn, and Bi respectively, wherein x is greater than 0 and equal to or less than 2 (or greater than 0 and less than 2), y is greater than 0 and equal to or less than 4, z is greater than 0 and equal to or less than 2, y+z is greater than 0 and equal to or less than 6, and x+y+z is greater than 0 and equal to or less than 7. More specifically, x may be 0.05 to 0.8, or 0.1 to 0.5, or 0.2 to 0.4, y may be 3.5 to 4, or 3.7 to 4, or 3.9 to 4, z may be 1.5 to 2, or 1.7 to 2, or 1.9 to 2. And, y+z may be 5 to 6, or 5.4 to 6, or 5.8 to 6, and x+y+z may be 5 to 6.8, or 6.1 to 6.8, or 6.2 to 6.8.
As explained above, the value of 7−(x+y+z) may be defined as the mole ratio of a vacancy remaining after filled with the above explained atoms, and it may be greater than 0, or greater than 0 and equal to or less than 0.2.
By fulfilling each mole ratio, the compound of one embodiment can maintain the unique crystal lattice structure, and yet, exhibit excellent phase stability due to the addition of an alkali metal, and exhibit low thermal conductivity because the alkali metal does not excessively fills the vacant lattice sites. Also, since the mole ratios of the alkali metal, Bi, etc. that donate electrons are optimized, the compound of one embodiment can exhibit more excellent electrical conductivity.
Since the chalcogen-containing compound of the above-explained one embodiment has low thermal conductivity, high electrical conductivity, and the resulting excellent thermoelectric conversion property, and high phase stability, it can be preferably used as a thermoelectric conversion material in various thermoelectric cooling systems, thermoelectric generation systems, etc.
Meanwhile, according to another embodiment of the present invention, a method for preparing the above-explained chalcogen-containing compound is provided. The preparation method includes the steps of: progressing a solid phase reaction of a mixture comprising raw materials comprising Sn, Bi and Se, and raw material comprising alkali metal (M); grinding the product of the solid phase reaction; and sintering the ground product.
In the preparation method, as the raw material comprising Sn, Bi and Se, for example, each powder of Sn, Bi and Se may be used, and as the raw material comprising alkali metal, although specifically limited, M2Se (M is an alkali metal) powder may be used.
And, each raw material may be mixed at a ratio corresponding to the mole ratio (x, y, z 7) of the Chemical Formula 1. For example, in case each Sn, Bi and Se powder and M2Se powder are used as raw materials, each raw material of M2Se, Sn, Bi and Se may be mixed at a mole ratio of x/2:y:z:7−x, considering that Se is also included in the raw material of M2Se.
The formation of the mixture of raw materials may be performed by adding each raw material at predetermined rates, then grinding or milling, and selectively pelletizing. The formed mixture may be in the state of a powder, pellet, ingot, etc. according to the process.
A solid phase state reaction step for such a mixture may be progressed. Such a solid phase reaction step may be conducted by various intermetallic reaction processes known before, and for example, it may be progressed at a temperature of 500 to 700° C. for each powder raw material. Heat treatment for such a solid phase reaction may be progressed in a furnace such as an electric furnace, etc., and it may be progressed under vacuum or inert gas atmosphere.
And, although the heat treatment and solid phase reaction may be progressed in a single step, they may be divided into two or more steps and progressed.
After the solid phase reaction, the reaction product is ground. Such a grinding step may be performed using a previously known method and apparatus for preparing a thermoelectric conversion material, and through the grinding step, a powder product may be obtained.
Meanwhile, between the solid phase reaction step and the grinding step, a step of cooling the product of the solid phase reaction step to form an ingot may be further performed. Here, the cooling may be performed using various cooling media, and any cooling devices and methods previously used in the preparation process of a thermoelectric conversion material may be used without specific limitations. After forming an ingot through the cooling step, the ingot may be ground.
After the grinding step, the ground product may be sintered. By performing the sintering step, a chalcogen-containing compound in the form of a sintered body may be prepared.
Such a sintering step may be performed by spark plasma sintering, etc. that are well known to a person having ordinary knowledge, and for example, it may be performed at a temperature of 550° C. or more and a pressure of 10 MPa or more. According to a more specific embodiment, the sintering step may be performed at a temperature of 550 to 700° C. and a pressure of 10 to 100 MPa for 5 to 10 minutes.
After performing the sintering, a cooling step may be further performed.
Since the above-explained steps may be performed by applying common preparation conditions, methods, and apparatuses for forming a metal compound such as a chalcogen compound or thermoelectric conversion material, and specific reaction conditions and methods are described in the examples below, additional explanations thereof are omitted.
According to yet another embodiment of the present invention, a thermoelectric element including the chalcogen-containing compound of the above embodiment as a thermoelectric conversion material is provided. Such a thermoelectric element may include the chalcogen-containing compound of the above embodiment (thermoelectric conversion material) as a p-type or n-type thermoelectric conversion material, and for this, it may include a compound additionally doped with an additional p-type or n-type element as a thermoelectric conversion material. The kind of the p-type element or n-type element or doping method that can be used is not specifically limited, and elements and doping methods commonly used to apply a thermoelectric conversion material as a p-type or n-type before may be used.
The thermoelectric element may include a thermoelectric element formed by processing and molding a p-type or n-type thermoelectric conversion material obtained in the form of a sintered body, and it may include an insulation substrate and electrode for the combination structure of the thermoelectric element, insulation substrate, and electrode, the structure of a common thermoelectric element may be applied.
As the insulation substrate, a sapphire substrate, a silicon substrate, a Pyrex substrate, a quartz substrate, etc. may be used, and as the electrode, any electrodes including metals or conductive metal compounds may be used.
Since the above-explained thermoelectric element includes the thermoelectric conversion material of one embodiment, it may exhibit an excellent thermoelectric conversion property, and may be preferably applied as a thermoelectric cooling system, thermoelectric generation system, etc. in various fields and uses.
According to the present invention, a novel chalcogen-containing compound that exhibits low thermal conductivity and excellent thermoelectric properties, and exhibits excellent phase stability even at relatively low temperature, and a method for preparing the same can be provided. By applying such a chalcogen-containing compound, a thermoelectric element exhibiting excellent properties can be provided.
The present invention will be explained in more detail in the following examples. However, these examples are presented only as illustrations of the present invention, and the scope of the present invention is not limited thereby.
Each powder of high purity raw materials of Sn, Bi, Se and Na2Se was weighed in a glove box at a mole ratio of 4:2:6.9 (7−0.1):0.1, put in a carbon crucible, and then charged into a quartz tube. The inside of the quartz tube was evacuated and sealed. The raw materials were maintained at a constant temperature in an electric furnace at 620° C. for 24 hours.
Thereafter, the quartz tube in which a reaction was performed was cooled with water to obtain an ingot, the ingot was finely ground to powder with a particle diameter of 75 μm or less, and sintered by spark plasma sintering (SPS) at a temperature of 620° C. and a pressure of 50 MPa for 10 minutes, thus preparing a chalcogen-containing compound of Na0.2Sn4Bi2Se7.
A chalcogen-containing compound of Na0.4Sn4Bi2Se7 was prepared by the same method as Example 1, except that each powder of high purity raw materials of Sn, Bi, Se and Na2Se was mixed in a glove box at a mole ratio of 4:2:6.8 (7−0.2):0.2.
A chalcogen-containing compound of Na0.75Sn4Bi1.7Se7 was prepared by the same method as Example 1, except that each powder of high purity raw materials of Sn, Bi, Se and Na2Se was mixed in a glove box at a mole ratio of 4:1.7:6.625 (7−0.375):0.375.
A chalcogen-containing compound of Sn4Bi2Se7 was prepared by the same method as Example 1, except that each powder of high purity raw materials of Sn, Bi and Se was mixed in a glove box at a mole ratio of 4:2:7.
1. Phase Analysis According to XRD Pattern
For the powder chalcogen-containing compounds immediately before the sintering process in Examples 1 to 3 and Comparative Example 1, X-ray diffraction analysis was performed and the results are shown in
And, using the TOPAS program, the lattice parameter of each powder chalcogen-containing compound of Examples 1 to 3 and Comparative Example 1 was calculated and is shown in the following Table 1.
In addition, for the powder chalcogen-containing compounds of Examples 1 to 3 and Comparative Example 1, the number of atoms for each component in the unit lattice is shown in the following Table 2.
First, referring to
And, referring to Table 1, in Examples 1 to 3, with the addition of alkali metal (Na), a lattice parameter increased compared to Comparative Example 1, and thus, it is inferred that the alkali metal fills a vacancy of the crystal lattice structure. Particularly, comparison of Examples 1 and 2 shows that a lattice parameter increases as the content of alkali metal increases, but Example 3 with relatively small Bi rate exhibits deceased lattice parameter compared to Example 2, and thus, it is confirmed that the alkali metal fills a vacancy of the crystal lattice structure, but since the atomic radius of the alkali metal (Na) is smaller than that of Bi, Example 3 exhibits decreased lattice parameter.
And, referring to Table 2, it is expected that in Examples 1 to 3 including an alkali metal, the concentration of the vacancy of the lattice structure decreases compared to Comparative Example 1, and that in Examples 1 and 2, the concentration of electrons increases due to electron donation by the alkali metal. Meanwhile, it is expected that in the case of Example 3 with decreased Bi content, the concentration of electrons decreases (the concentration of holes increases) because Na+ donates two less electrons compared to Bi3+.
Referring to is generated, thus forming many secondary phases (Bi3Se4, Bi8Se9, Sn3Bi9Se13) (The peaks resulting from the many secondary phases are confirmed in XRD pattern). To the contrary, it is confirmed that the compounds of Examples 1 to 3 maintain face-centered cubic lattice structures without generation of secondary phases, and exhibit excellent phase stability. Thus, it is confirmed that the compounds of Examples 1 to 3 exhibit excellent phase stability even at a relatively low temperature.
2. Temperature Dependency of Electrical Conductivity
For the chalcogen-containing compound specimens prepared in Examples 1 to 3, electrical conductivities were measured according to temperature change and are shown in
Referring to
3. Measurement of Seebeck Coefficient and Temperature Dependency of Seebeck Coefficient
For the chalcogen-containing compound specimens prepared in Examples 1 to 3, Seebeck coefficients (S) were measured according to temperature change and are shown in
As shown in
However, comparing Examples 1 and 2, it is confirmed that as the content of an alkali metal increases from 0.2 to 0.4, the Seebeck coefficient changes from a positive (+) to a negative (−) value. It means that the main charge carrier of material is changed from holes to electrons due to the additional electron donation by the alkali metal, and indicates property change from P-type to N-type semiconductor material. It means that the main charge carrier in Example 1 is hole despite the additional electron donation by the alkali metal. As in Example 3, if the content of Bi decreases and the content of an alkali metal increases, the alkali metal donates less electrons compared to the Bi decrease, thus exhibiting P-type material property like Example 1.
4. Temperature Dependency of Output Factor
For the chalcogen-containing compound specimens prepared in Examples 1 to 3, output factors were calculated according to temperature change and are shown in
The output factor is defined as power factor (PF)=σS2, and it was calculated using the values of σ (electrical conductivity) and S (Seebeck coefficient) shown in
As shown in
5. Temperature Dependency of Thermal Conductivity and Lattice Thermal Conductivity
For the chalcogen-containing compound specimens prepared in Examples 1 to 3, thermal conductivities and lattice thermal conductivities were measured according to temperature change and are shown in
Further, total thermal conductivity (k=kL+kE) is divided into lattice thermal conductivity (kL) and thermal conductivity (kE) calculated according to Wiedemann-Franz law (kE=LσT), wherein, as the Lorentz number (L), a value calculated from the Seebeck coefficient according to temperature was used.
Referring to
6. Temperature Dependency of Thermoelectric Figure of Merit (ZT)
For the chalcogen-containing compound specimens prepared in Examples 1 to 3, the thermoelectric figures of merit were calculated according to temperature change and are shown in
Referring to
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2016-0142891 | Oct 2016 | KR | national |
| 10-2017-0134204 | Oct 2017 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2017/011479 | 10/17/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/080085 | 5/3/2018 | WO | A |
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| 6013204 | Kanatzidis et al. | Jan 2000 | A |
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| 20160099396 | Lee et al. | Apr 2016 | A1 |
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| 10-2014-0116668 | Oct 2014 | KR |
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| Number | Date | Country | |
|---|---|---|---|
| 20190288172 A1 | Sep 2019 | US |
