CN103872237A - Copper-sulfur-based high-performance thermoelectric material and preparation method thereof - Google Patents
Copper-sulfur-based high-performance thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 13
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 239000010949 copper Substances 0.000 claims description 65
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- 238000010791 quenching Methods 0.000 claims description 16
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010248 power generation Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
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Abstract
The invention relates to a copper-sulfur-based high-performance thermoelectric material and a preparation method thereof, and particularly provides a novel p-type thermoelectric compound Cu(2-x)S or Cu2S(1-y)Ay (A is Se or Te) and a preparation method thereof. The compound is composed of Cu-S-(Se/Te), x equals 0.02-0.05, and y equals 0.2-0.4. The material is a semiconductor. Compared with traditional thermoelectric materials, the compound is simple, low in cost of raw materials, high in Seebeck coefficient, low in thermal conductivity, and excellent in thermal property, the thermoelectric figures of merit ZT of some components can reach 1 and above at 800K, and the compound has good thermoelectric application prospects.
Description
Technical field
The present invention relates to copper sulfenyl high performance thermoelectric material and preparation method thereof, specifically, the present invention relates to a kind of novel p-type thermoelectric compound Cu
2-xs
1-ya
y(for example, Cu
2-xs and Cu
2s
1-ya
y, in formula, A is Se or Te) and preparation method thereof, described p-type thermoelectric compound consist of Cu
2-xs
1-y(Se/Te)
y, the value that wherein value of x is 0.02～0.05, y is 0.2～0.4.
Copper sulfenyl high performance thermoelectric material of the present invention is a kind of semiconductor, than traditional thermoelectric material, the composition of this compound is simple, cost of material is cheap, there is higher Seebeck coefficient and extremely low thermal conductivity, thermoelectricity capability excellence, part thermoelectric figure of merit ZT in the time of 800K, can reach 1.0 and more than, there is good thermoelectric applications prospect.
Technical background
Because of the appearance of thorny problem such as go from bad to worse of the exhaustion of non-renewable energy resources and environment, the exploitation of new cleaning fuel receive much concern, thermo-electric converting material utilizes its Seebeck effect and paltie effect can realize the mutual conversion between heat energy and electric energy, it is a kind of novel clean energy resource, it can use the natural temperature difference and industrial waste heat, cogeneration, also can be made into noiseless, without transmission device, refrigeration machine that reliability is high.But, because of the conversion efficiency of thermoelectric material very low (<10% conventionally), not yet can realize large-scale commercialization at present, therefore, the thermoelectricity capability that how to improve thermoelectric material is an of great value research topic.
The conversion efficiency of thermoelectric material is determined by high low side temperature and the material essence performance of material work.For definite environment for use, high low side temperature normally determine, institute think improve conversion efficiency can only from optimize material itself start with.Conventionally the quality of assessing thermoelectric material energy conversion efficiency with dimensionless thermoelectric figure of merit ZT, its definition is: ZT=S
2t σ/κ, wherein S is thermoelectric potential (Seebeck (Seekbeck) coefficient), and T is absolute temperature, and σ is conductivity, and κ is thermal conductivity.In order to obtain high thermoelectric efficiency, just require material must there is high thermoelectric figure of merit.
The thermoelectric material that has started at present application mostly is metallic compound and solid solution thereof, as Bi
2te
3, SiGe, PbTe etc., but the preparation condition of these thermoelectric materials has relatively high expectations, and need under certain protection gas, carry out, and contains harmful heavy metal, and because ZT value is all about 1.0, so that the shortcoming such as energy conversion efficiency is not high.
In recent decades; researchers are by various means; as adulterated, reduce the dimension (making film, nano wire, quantum dot etc.) of material and find the methods such as noval chemical compound the significantly lifting that has realized thermoelectric material thermoelectricity capability; ZT value can reach more than 1.5, for the scale of thermoelectric material should be used as further propelling.
Copper sulfur-based compound Cu
2-xs is a kind of novel thermoelectric material, and its chemical formula is extremely simple, but its crystal structure and atomic arrangement situation are very complicated.As Cu
2-xthere is the solid phase phase transformation of two places in S, and phase transition temperature is relevant with x value near 370K, 700K.370K is γ phase (durleite (lowchalcocite): L-chalc) below, and 370K to 700K is β phase (high vitreous copper (high chalcocite): H-chalc), 700K is α phase above.The phase structure of low temperature γ phase (L-chalc) is extremely complicated, although carried out the research of nearly decades, its crystal structure is still very not bright and clear so far, generally believes at present it is rhombic system, contains 96 Cu in each structure cell
2s unit, but each Cu has well-determined position; High temperature β phase (H-chalc) is hexagonal crystal system, contains two Cu in each structure cell
2s unit, wherein S presses Hexagonal array, and Cu is randomly dispersed in Wyckoff position (represent in structure cell atom of equal value symmetric) with certain probability.High temperature β phase (H-chalc) is fast-ionic conductor, has very high mobility, but high temperature β phase (H-chalc) becomes the reason of fast-ionic conductor and other fast-ionic conductors as metal halogen compound (AgCl, AgBr, AgI, CaF
2) difference, Cu
2it is not to have had high animal migration because the increase of Frenkel disorder number under high temperature causes ion that S has fast-ionic conductor characteristic, but because at Cu
2the position that can occupy for Cu ion in S is more than the number of Cu ion, and Cu ion can move freely in different interstitial sites, so at relatively low temperature, Cu
2the β phase (H-chalc) of S has just had the character of class I liquid I.
Cu
2-xin S, because Cu room shows p-type electric-conducting behavior, and conductivity increases with the increase of x value.In the time that x is 0, meet the Cu of stoichiometric proportion
2the behavior of S performance semiconductor, because its energy gap is about 1.2eV, is the ideal material of solar cell, can form the good (Cu that contacts with CdS again
2s/CdS), so to Cu
2the research of S class material focuses mostly on aspect battery, very few to the research of thermoelectricity capability, only in a small amount of document, reports that such material had larger thermoelectric potential and very low thermal conductivity, to Cu
2-xthe thermoelectricity capability of S material is studied further and is optimized, probably this Cu
2-xs sill will have good thermoelectric applications prospect.
Experimental studies have found that the Cu of intrinsic
2s has extremely low heat conductivity value, is only 0.3～0.4Wm in the probe temperature interval of 300～800K
-1k
-1, but because its carrier concentration is too low, make its conductivity value in the time approaching 650K with regard to not enough 100Sm
-1, because the too small reason of power factor (PF) cannot have good thermoelectricity capability.So, there is so low thermal conductivity based on this type of copper sulfur-based compound, the carrier concentration of attempting regulating and controlling by means such as doping this base thermoelectricity material, obtains preferably power factor (PF), thereby realizes the raising to its thermoelectricity capability.
Summary of the invention
For this reason, the invention provides a kind of p-type thermoelectric compound, the general formula of described compound is Cu
2-xs
1-ya
y, in formula, A is selected from Se and/or Te, and x value is between 0.02 to 0.05, and y value is between 0.2 to 0.4.
Again, the invention provides a kind of p-type thermoelectric compound, the general formula of described compound is Cu
2-xs or Cu
2s
1-ya
y, in formula, A is selected from Se and/or Te, and x value is between 0 to 0.05, and y value is between 0 to 0.4.
In an embodiment of the invention, x value is between 0.02 to 0.05, and y value is between 0.2 to 0.3.
In an embodiment of the invention, x value is between 0.02 to 0.05, and y value is between 0.2 to 0.4.
On the other hand, the invention provides a kind of method of preparing p-type thermoelectric compound of the present invention, described method comprises:
(1) with general formula Cu
2-xs or Cu
2s
1-ya
ystoichiometric proportion (2-x): (1-y): y weighs respectively each element simple substance as initial feed;
(2) initial feed being mixed to final vacuum is encapsulated in quartz ampoule;
(3) by initial feed melting;
(4) carry out Quenching Treatment, obtain the rear block that quenches;
(5) block after described quenching is pulverized, and be cold-pressed into be again packaged in after block and in quartz ampoule, carry out annealing in process; With
(6) be cooled to room temperature, obtain p-type thermoelectric compound.
In the present invention, described method also comprises pulverizes p-type thermoelectric compound, and carries out plasma discharging pressure sintering in mould, obtains the p-type thermoelectric compound being shaped.
In an embodiment of the invention, described each element simple substance is respectively elemental copper, sublimed sulfur and simple substance Se and/or Te.
In an embodiment of the invention, in step (2), described Vacuum Package using plasma or flame gun in argon gas atmosphere glove box are carried out.
In an embodiment of the invention, in step (2), it is 1-10000Pa that quartz ampoule vacuumizes rear internal pressure.
In an embodiment of the invention, in step (3), described in be melted in vertical melting furnace and carry out: be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, constant temperature melting 20 hours.
In an embodiment of the invention, in step (4), described quenching is carried out in mixture of ice and water.
In an embodiment of the invention, in step (5), described annealing process carries out in tubular annealing stove: 5-7 days anneals at 580 DEG C.
In an embodiment of the invention, described mould is graphite jig, and, mould inside and on push-down head place spraying boron nitride (BN) to insulate; Sintering temperature is 390-420 DEG C, and pressure is 50-65MPa, sintering time 5-10 minute.
On the one hand, the invention provides the application of p-type thermoelectric compound of the present invention in thermoelectric device again.Described thermoelectric device comprises thermoelectric power generation or the thermoelectric cooling unit of middle high-temperature region, as in vehicle exhaust and industrial production, and the particularly thermoelectric power generation of the middle high-temperature region in metallurgy industry or thermoelectric cooling unit.
In the present invention, this p-type thermoelectric compound is suitable for the thermoelectric power generation of middle high-temperature region or the use of thermoelectric cooling, as in vehicle exhaust and industrial production, particularly in metallurgy industry, utilize its high-temperature residual heat used heat to generate electricity, can realize effective utilization of low-density thermal source, reach to a certain extent the object of energy-saving and emission-reduction.
Specifically, the invention provides a kind of novel p-type thermoelectric compound and preparation method thereof, it consists of Cu
2-xs
1-y(Se/Te)
y, wherein x value is between 0 to 0.05, and y value is between 0 to 0.4.
In the present invention, described part is through the Cu of carrier concentration regulation and control
2-xs
1-y(Se/Te)
ythe thermoelectric figure of merit ZT of compound in the time of 800K, can reach 1.0 and more than, be applicable to the application of middle high-temperature region.And, described Cu
2-xs
1-y(Se/Te)
ycompound focus material has higher Seebeck coefficient and extremely low thermal conductivity.
Thermoelectric compound material C u of the present invention
2-xs exists by the general solid phase phase transformation that class I liquid I changes mutually in opposite directions between 370-400K; And between 650-700K, there is another solid phase phase transformation.
The Seebeck coefficient of material of the present invention increases gradually with the rising of temperature, and conductivity is with the non-monotonic variation of rising of temperature, and near solid phase phase transition temperature, the variation tendency of conductivity changes.Meanwhile, thermal conductivity maintains reduced levels always, makes its thermoelectric figure of merit can reach 1.0 left and right in the time of 800K, and thermoelectricity capability is better.
In addition, the raw material source that preparation method of the present invention adopts is abundant, and with low cost, production technology and production equipment are simple, and controllability and repeatability are all better.
Brief description of the drawings
Fig. 1 is preparation method's of the present invention schematic flow sheet.
Fig. 2 is thermoelectric compound (Cu in one embodiment of the present invention
1.98s) thermoelectricity capability.
Wherein, Fig. 2 (a) is the conductivity of thermoelectric compound; Fig. 2 (b) is the Seebeck coefficient of thermoelectric compound; Fig. 2 (c) is the thermal conductivity of thermoelectric compound, and Fig. 2 (d) is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 3 is thermoelectric compound (Cu in another execution mode of the present invention
1.95s) thermoelectricity capability.
Wherein, Fig. 3 (a) is the conductivity of thermoelectric compound; Fig. 3 (b) is the Seebeck coefficient of thermoelectric compound; Fig. 3 (c) is the thermal conductivity of thermoelectric compound, and Fig. 3 (d) is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 4 is thermoelectric compound (Cu in another execution mode of the present invention
2s
0.7te
0.3) thermoelectricity capability.
Wherein, Fig. 4 (a) is the conductivity of thermoelectric compound; Fig. 4 (b) is the Seebeck coefficient of thermoelectric compound; Fig. 4 (c) is the thermal conductivity of thermoelectric compound, and Fig. 4 (d) is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 5 is thermoelectric compound (Cu in another execution mode of the present invention
2s
0.6se
0.4) thermoelectricity capability.
Wherein, Fig. 5 (a) is the conductivity of thermoelectric compound; Fig. 5 (b) is the Seebeck coefficient of thermoelectric compound; Fig. 5 (c) is the thermal conductivity of thermoelectric compound, and Fig. 5 (d) is the thermoelectric figure of merit ZT of thermoelectric compound.
Fig. 6 is thermoelectric compound (Cu in an embodiment of the present invention
2s
0.7te
0.3) X-ray diffraction (XRD) collection of illustrative plates of powder.
Embodiment:
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.It should be noted that content of the present invention is not limited to these concrete execution modes.Do not deviating under the prerequisite of background of the present invention and spirit, those skilled in the art can carry out substitutions and modifications of equal value on the basis of reading content of the present invention, and its content is also included within the scope of protection of present invention.
The invention provides a kind of novel p-type thermoelectric compound and preparation method thereof, wherein:
● the compound of synthesized of the present invention is Cu
2-xs
1-y(Se/Te)
y, being formed by element Cu and element S, Se/Te, x value is between 0.02 to 0.05, and y value is between 0.2 to 0.4.
● preparation process of the present invention realizes by Vacuum Package, melting, quenching, annealing process, Figure 1 shows that process chart prepared by this material.
● preparation method of the present invention is using pure element simple substance as initial feed, is respectively elemental copper, sublimed sulfur and simple substance Se/Te.Initial feed is with stoichiometric proportion (2-x): 1-y:y weighs, and is then sealed in quartz ampoule.
● Vacuum Package is carried out in argon gas atmosphere glove box, using plasma or flame gun packaged type, and when encapsulation, quartz ampoule vacuumizes, and internal pressure has 1-10000Pa.
● melting process carries out in vertical melting furnace.Be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, constant temperature melting was quenched in mixture of ice and water after 20 hours.
● annealing process carries out in tubular annealing stove.First the block after quenching is clayed into power in agate mortar, then be cold-pressed into block, Vacuum Package, in quartz ampoule, is annealed 1 hour-7 days at 580 DEG C again, cools to room temperature with the furnace.
● the block after annealing is milled to powder in agate mortar, then carries out plasma discharging pressure sintering.Adopt graphite jig, and mould inside and on push-down head place spraying BN with insulation; Sintering temperature is 390-420 DEG C, and pressure is 50 or 65MPa, sintering time 5-10 minute.
Embodiment 1:
Cu
1.88S（x=0.02,y=0）
The mol ratio weighing that simple substance raw material Cu and S are pressed to 1.98:1, is then packaged in quartz ampoule.Be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, by raw material melting 20 hours at 1150 DEG C, then quench in mixture of ice and water.The block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is again packaged in quartz ampoule, finally puts it in tube furnace and at 580 DEG C, anneals 7 days, is then chilled to room temperature with stove again.
The product that obtains after annealing is pulverized, carry out discharge plasma sintering (SPS sintering), sintering temperature is 390-420 DEG C, and pressure is 50 or 65MPa, and sintering time is 5-10 minute, finally obtains fine and close block materials.
As shown in Figure 2, gained Cu
1.98the thermoelectricity capability measurement of S block materials shows that this material has very high Seebeck coefficient in institute temperature measuring area (300-800K), and moderate conductivity.And this material has abnormal low thermal conductivity: in 300-800K temperature range, and its numerical value < 0.6Wm
-1k
-1.The ZT value that calculates this material according to performance measurement can reach 1.0 in the time of 800K.
Embodiment 2:
Cu
1.95S（x=005,y=0）
The mol ratio weighing that simple substance raw material Cu and S are pressed to 1.95:1, is then packaged in quartz ampoule.Be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, by raw material melting 20 hours at 1150 DEG C, then quench in mixture of ice and water.The block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is again packaged in quartz ampoule, finally puts it in tube furnace and at 580 DEG C, anneals 7 days, is then chilled to room temperature with stove again.
The product obtaining after annealing is pulverized, carry out discharge plasma sintering, sintering temperature is 390-420 DEG C, and pressure is 65MPa, and sintering time is 5-10 minute, finally obtains fine and close block materials.
As shown in Figure 3, gained Cu
1.95the thermoelectricity capability measurement of S block materials shows that its Seebeck coefficient of sample of this composition is a little less than Cu
1.98s, conductivity is slightly high.And the thermal conductivity of the sample of this composition is all greater than Cu in corresponding warm area
1.98s, but its heat conductivity value also maintains very low level: in 300-800K temperature range, its numerical value < 0.8Wm
-1k
-1.The ZT value that calculates the material of this composition according to performance measurement can arrive 0.7 in the time of 800K.
Embodiment 3:
Cu
2S
.07Te
0.3（x=0,y=0.3）
The mol ratio weighing that simple substance raw material Cu, S and Te are pressed to 2:0.7:0.3, is then packaged in quartz ampoule.Be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, by raw material melting 20 hours at 1150 DEG C, then quench in mixture of ice and water.The block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is again packaged in quartz ampoule, finally puts it in tube furnace and at 580 DEG C, anneals 7 days, is then chilled to room temperature with stove again.
The product that obtains after annealing is pulverized, carry out discharge plasma sintering, sintering temperature is 390-420 DEG C, and pressure is 50 or 65MPa, and sintering time is 5-10 minute, finally obtains fine and close block materials.
As shown in Figure 4, gained Cu
2s
0.7te
0.3the thermoelectricity capability measurement of block materials shows, the sample of this composition has good thermoelectricity capability, and its heat conductivity value also maintains quite low level: in 300-800K temperature range, and its numerical value < 0.41Wm
-1k
-1.The ZT value that calculates the material of this composition according to performance measurement can arrive 1.2 in the time of 800K.
Embodiment 4:
Cu
2S
0.6Se
0.4（x=0，y=0.4）
The mol ratio weighing that simple substance raw material Cu, S and Se are pressed to 2:0.6:0.4, is then packaged in quartz ampoule.Be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, by raw material melting 20 hours at 1150 DEG C, then quench in mixture of ice and water.The block obtaining after quenching is pulverized in agate mortar, powder is cold-pressed into bulk, is again packaged in quartz ampoule, finally puts it in tube furnace and at 580 DEG C, anneals 7 days, is then chilled to room temperature with stove again.
The product that obtains after annealing is pulverized, carry out discharge plasma sintering, sintering temperature is 390-420 DEG C, and pressure is 50 or 65MPa, and sintering time is 5-10 minute, finally obtains fine and close block materials.
As shown in Figure 5, gained Cu
2s
0.6se
0.4the thermoelectricity capability measurement of block materials shows, the thermoelectricity capability of this composition sample is also better, but is inferior to Cu
2s
0.7te
0.3.Its heat conductivity value also maintains quite low level: in 300-800K temperature range, and its numerical value < 0.48Wm
-1k
-1.The ZT value that calculates the material of this composition according to performance measurement can arrive 0.8 in the time of 800K.
Claims (14)
1. a p-type thermoelectric compound, the general formula of described compound is Cu
2-xs or Cu
2s
1-ya
y, in formula, A is Se and/or Te, and x value is between 0 to 0.05, and y value is between 0 to 0.4.
2. p-type thermoelectric compound as claimed in claim 1, is characterized in that, x value is between 0.02 to 0.05, and y value is between 0.2 to 0.4.
3. p-type thermoelectric compound as claimed in claim 1, is characterized in that, x value is between 0 to 0.03, and y value is between 0.1 to 0.4.
4. a method of preparing p-type thermoelectric compound described in claim 1-3 any one, described method comprises:
(1) with general formula Cu
2-xs or Cu
2s
1-ya
ystoichiometric proportion weigh respectively each element simple substance as initial feed;
(2) initial feed being mixed to final vacuum is encapsulated in quartz ampoule;
(3) by initial feed melting;
(4) carry out Quenching Treatment, obtain the rear block that quenches;
(5) block after described quenching is pulverized, and be cold-pressed into be again packaged in after block and in quartz ampoule, carry out annealing in process;
(6) be cooled to room temperature, obtain p-type thermoelectric compound.
5. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, gained p-type thermoelectric compound is pulverized, and carries out plasma discharging pressure sintering in mould, obtains the p-type thermoelectric compound being shaped.
6. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, described each element simple substance is respectively elemental copper, sublimed sulfur and simple substance Se and/or Te.
7. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, in step (2), described Vacuum Package using plasma or flame gun in argon gas atmosphere glove box are carried out.
8. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, in step (2), it is 1-10000Pa that quartz ampoule vacuumizes rear internal pressure.
9. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, in step (3), described in be melted in vertical melting furnace and carry out: be warming up to 1150 DEG C with the heating rate of 4.5 DEG C/min, constant temperature melting 20 hours.
10. the method for preparing as claimed in claim 4 p-type thermoelectric compound, is characterized in that, in step (4), described quenching is carried out in mixture of ice and water.
11. prepare the method for p-type thermoelectric compound as claimed in claim 4, it is characterized in that, in step (5), described annealing process carries out in tubular annealing stove: 5-7 days anneals at 580 DEG C.
12. prepare the method for p-type thermoelectric compound as claimed in claim 5, it is characterized in that, described mould is graphite jig, and, mould inside and on push-down head place spraying boron nitride (BN) to insulate; Sintering temperature is 390-420 DEG C, and pressure is 50-65MPa, sintering time 5-10 minute.
13. application of p-type thermoelectric compound in thermoelectric device as described in claim 1-3 any one.
14. application as claimed in claim 13, described thermoelectric device comprises thermoelectric power generation or the thermoelectric cooling unit of middle high-temperature region, as in vehicle exhaust and industrial production, the particularly thermoelectric power generation of the middle high-temperature region in metallurgy industry or thermoelectric cooling unit.
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