CN101570321A - Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure - Google Patents
Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure Download PDFInfo
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- CN101570321A CN101570321A CNA2009100624235A CN200910062423A CN101570321A CN 101570321 A CN101570321 A CN 101570321A CN A2009100624235 A CNA2009100624235 A CN A2009100624235A CN 200910062423 A CN200910062423 A CN 200910062423A CN 101570321 A CN101570321 A CN 101570321A
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Abstract
The invention relates to a method for preparing a thermoelectric material. The method for preparing a BixSbyTe(3-z) thermoelectric material with high performance and nano structure is characterized by comprising the following steps: 1) using marketable Bi(2-x)SbxTe3 as an initial raw material (wherein x is more than 0 and less than 2), and pressing the initial raw material into a block; 2) melting the block Bi(2-x)SbxTe3 to obtain a melt, and carrying out strip throwing treatment for the melt to obtain a thin strip material; 3) crushing the thin strip material into powder, filling the powder into a graphite jig, compacting the powder, and then putting the powder and the graphite jig together into a discharge plasma sintering furnace to sinter, wherein the sintering process comprises that the vacuum degree is kept below 10Pa, the temperature raising speed is 40 to 100 DEG C per minute, the sintering temperature is between 350 and 500 DEG C, and the pressure is 20 to 200MPa, the sintering time is 4 to 6 minutes; and after the sintering is finished, cooling the material to room temperature along with the furnace to form the BixSbyTe(3-z) thermoelectric material with the high performance and the nano structure. The optimal thermoelectric performance value ZT of the obtained BixSbyTe(3-z) thermoelectric material with the nano structure reaches more than 1.0 at the temperature between 30 and 150 DEG C, and the maximum value reaches 1.2 to 1.6 at the temperature between 60 and 100 DEG C.
Description
Technical field
The preparation method who the present invention relates to a kind of thermoelectric material is (to Bi
2-xSb
xTe
3Thermoelectric material carries out modification), belong to the new energy materials field.
Background technology
Thermoelectric generation technology is to utilize the Sai Beike of semiconductor material (Seebeck) effect and Pa Er card (Peltier) effect to carry out the directly technology of conversion of energy, and efficiency of conversion depends primarily on the zero dimension performance index ZT value (ZT=of material
2T/ wherein is the Seebeck coefficient; Be specific conductivity; T is an absolute temperature; Be thermal conductivity).Owing to do not contain the needed huge transmission rig of conventional energy transformation technology, thereby have that volume is little, reliability is high, manufacturing and characteristics such as running cost is low, the life-span long, manufacturing process is simple, application surface is very wide, thereby, be expected wide model and be applied to a large amount of and disperse the thermoelectric power generation of the low density heat energy (as solar heat, refuse burner waste heat, factory's heat extraction and vehicle exhaust heat extraction etc.) that exists as a kind of novel, the environmental harmony type clear energy sources switch technology of 21st century.In addition, at aerospace, ocean exploitation, fields such as military particular power source also have broad application prospects.
The Tellurobismuthite compound is to study the earliest, also is to develop one of the most sophisticated thermoelectric material at present, is widely used in the generating of refrigeration device and cold zone.The prepared Tellurobismuthite compound maximum heat electrical property figure of merit ZT of traditional technology (zone melting method) is 0.8～1, and therefore the research emphasis for bismuth telluride thermoelectric material is to seek new technology, to obtain the block materials of thermoelectricity capability excellence.
Summary of the invention
The object of the present invention is to provide a kind of high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material, the thermoelectricity capability figure of merit height of the thermoelectric material of this method preparation.
To achieve these goals, technical scheme of the present invention is: a kind of high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material is characterized in that it comprises the steps:
1) with commercially available Bi
2-xSb
xTe
3Be initial feed, wherein 0＜x＜2; On tabletting machine with Bi
2-xSb
xTe
3Be pressed into block;
2) with the Bi of block shape
2-xSb
xTe
3Pack in the quartz glass tube of single roller fast cooling device, under the argon gas atmosphere protection, earlier under high-frequency induction heating with the Bi in the quartz glass tube
2-xSb
xTe
3Fusion obtains melt; In argon gas atmosphere, the argon gas spraying pressure is under 500～5000r/min greater than the copper roller speed of rotation of 0.01MPa, single roller fast cooling device, and melt is got rid of tape handling, obtains having the Bi of nanostructure then
xSb
yTe
3-z(0＜x＜2, x+y=2 ,-0.2＜z＜0.2) thin band material;
3) thin band material is milled be ground into powder, the compacting in the graphite jig of packing into, put into discharge plasma sintering (SPS) stove (equipment) together with graphite jig then and carry out sintering, sintering process is: vacuum tightness remains on below the 10Pa, heat-up rate is 40～100 ℃/min, sintering temperature is 350～500 ℃, and pressure is 20～200MPa, and sintering time is 4～6min; Sintering cools to room temperature with the furnace after finishing, and obtains high performance and nano structure Bi
xSb
yTe
3-z(0＜x＜2, x+y=2 ,-0.2＜z＜0.2) thermoelectric material (nanostructure size＜500nm, and it is nanocrystalline greater than 5% amorphous and 5～20nm to have a volume content).
The electric current of described high-frequency induction heating is that 2～11A, voltage are 100～500V.
The speed of cooling of single roller quench (liquid phase quench) is controlled at 10
5～10
6℃/sec between, the speed of rotation of speed of cooling by the copper roller regulated, corresponding copper roller rotating speed is 500～5000r/min, the strip width that obtains is approximately 1～3mm, thickness is approximately 5～60 μ m; The contact copper roll surface of strip is no crystalloid, and strip free surface (not contacting the copper roll surface) is dendritic.
Heating mode comprises manual regulation and automatic the adjusting in described discharge plasma sintering (SPS) the stove sintering process, and pressuring method comprises that preceding plus-pressure of intensification and intensification back are before being sintered the material densification.
When the speed of rotation of copper roller was 500～5000r/min, the SPS sintering temperature was 350～500 ℃, when sintering time is 4～6min, and the nanostructure Bi that obtains
xSb
yTe
3-zThe thermoelectricity capability figure of merit ZT of thermoelectric material reaches more than 1.0 at 30～150 ℃, and to reach maximum value near 60～100 ℃ be 1.2～1.6.
So-called single roller quench, be initial feed to be heated into uniform melt by the ratio-frequency heating mode, melt is blown from quartz glass tube under certain argon gas spraying pressure, fall on the copper roller rotating at full speed and be thrown out of, change the speed of cooling of melt by the speed of rotation of regulating argon gas spraying pressure and copper roller, thereby obtain the thin ribbon shaped sample of different size.This preparation technology's distinguishing feature is that resulting sample crystal grain is tiny.
So-called discharge plasma sintering (Spark Plasma Sintering, be called for short SPS), be by graphite pressure head up and down under vacuum condition, utilizing pulsed current direct heating and surface active in the sintered compact pressurization, the quick densifying of realization material under relatively low temperature and very short time.Compare with traditional sintering method, can save energy, improve equipment efficient, reduce cost and prepared block materials uniform crystal particles, density height.
Implementing key of the present invention is the control of single roller quench rate of cooling and the sintering process system of discharge plasma sintering (SPS).
The invention has the beneficial effects as follows:
1) the thermoelectricity capability figure of merit ZT of the thermoelectric material that obtains of this method reaches more than 1.0 thermoelectricity capability figure of merit height.
2) technology is simple, and processing parameter is controlled easily; Employing discharge plasma agglomerating temperature is low, the time short, the energy-and time-economizing.
Description of drawings
Fig. 1 is the strip sample of embodiment 1,2 and 3 and the X ray diffracting spectrum of Qu Rong sample;
Fig. 2 A is the strip sample contact picture of embodiment 2;
Fig. 2 B is the strip sample free surface figure of embodiment 2;
Fig. 2 C is field emission scanning electron microscope (FESEM) photo of block sample behind embodiment 2 sintering;
Fig. 3 a is high-resolution-ration transmission electric-lens (HRTEM) photo of the strip sample of embodiment 2;
Fig. 3 b is high-resolution-ration transmission electric-lens (HRTEM) photo of block sample behind the sintering of embodiment 2;
Fig. 4 a is the graph of a relation of embodiment 1,2 and 3 prepared block sample thermoelectricity capabilities (specific conductivity) and temperature;
Fig. 4 b is the graph of a relation of embodiment 1,2 and 3 prepared block sample thermoelectricity capabilities (Seebeck coefficient) and temperature;
Fig. 4 c is the graph of a relation of embodiment 1,2 and 3 prepared block sample thermoelectricity capabilities (thermal conductivity) and temperature;
Fig. 4 d is the graph of a relation of embodiment 1,2 and 3 prepared block sample thermoelectricity capabilities (thermoelectric figure of merit ZT) and temperature.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
A kind of high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material is (to commercially available Bi
0.48Sb
1.52Te
3Carry out modification), it comprises the steps:
1) Bi for preparing with zone melting method
0.48Sb
1.52Te
3Alloy (commercially available) is an initial feed, takes by weighing 5g Bi
0.48Sb
1.52Te
3, put it in the steel die that diameter is 10mm and on tabletting machine, be pressed into block;
2) block that presses is packed in the quartz glass tube of single roller fast cooling device, under the argon gas atmosphere protection, earlier under high-frequency induction heating (electric current is that 8A, voltage are 200V) with the Bi in the quartz glass tube
0.48Sb
1.52Te
3Fusion obtains melt; In argon gas atmosphere, the argon gas spraying pressure is under the 4000r/min greater than the copper roller speed of rotation of 0.12MPa, single roller fast cooling device, and melt is got rid of tape handling, obtains having the Bi of nanostructure then
0.48Sb
1.52Te
3-zThin band material (width is that 1～2mm, thickness are 15～20 μ m); Shown in Fig. 1 (embodiment 1), strip is monophasic Bi
2Te
3Type structure (Bi
xSb
yTe
3-zX+y=2, ,-0.2＜z＜0.2, x no matter, what value y gets, and its structure does not change, so, be called monophasic Bi at this
2Te
3The type structure).
3) thin band material is milled be ground into powder, the compacting in the graphite jig of 15mm of packing into, put into discharge plasma sintering (SPS) stove together with graphite jig then and carry out sintering, sintering process is: under＜10Pa vacuum condition, heat-up rate is 100 ℃/min, sintering temperature is 500 ℃, and pressure is 20MPa, and sintering time is 5min; Sintering cools to room temperature with the furnace after finishing, and obtains the fine and close high performance and nano structure Bi with nanostructure
xSb
yTe
3-z(3-z=2.8～3.2 are because composition has partial ununiformity for x=0.48, y=1.52) thermoelectric material sample (nanostructure size＜500nm, and it is nanocrystalline greater than 5% amorphous and 5～20nm to have a volume content).
To the high performance and nano structure Bi that obtains
xSb
yTe
3-zAfter polished finish is carried out on the surface of thermoelectric material sample, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.To the high performance and nano structure Bi that obtains
xSb
yTe
3-zRectangular parallelepiped and thickness that the thermoelectric material sample cuts into 2mm * 2mm * 8.0mm are the disk of 1.5mm, be used to measure Sai Beike (Seebeck) coefficient, specific conductivity and thermal conductivity, see Fig. 4 a, Fig. 4 b, Fig. 4 c, illustrated as can be known that by Fig. 4 d thermoelectricity capability figure of merit ZT that embodiment 1 obtains is at wide temperature range Nei Keda 1.4.
Embodiment 2:
A kind of high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material is (to commercially available Bi
0.52Sb
1.48Te
3Carry out modification), it comprises the steps:
1) Bi for preparing with zone melting method
0.52Sb
1.48Te
3Alloy (commercially available) is an initial feed, takes by weighing 5g Bi
0.52Sb
1.48Te
3, put it in the steel die of 10mm and on tabletting machine, be pressed into block;
2) block that presses is packed in the quartz glass tube of single roller fast cooling device, under the argon gas atmosphere protection, earlier under high-frequency induction heating (electric current is that 8A, voltage are 200V) with the Bi in the quartz glass tube
0.52Sb
1.48Te
3Fusion obtains melt; In argon gas atmosphere, the argon gas spraying pressure is under the 4000r/min greater than the copper roller speed of rotation of 0.12MPa, single roller fast cooling device, and melt is got rid of tape handling, obtains having the Bi of nanostructure then
xSb
yTe
3-z(width is that 1～2mm, thickness are 15～20m) to (x=0.52, y=1.48,3-z=2.9～3.1) thin band material; Shown in Fig. 1 (embodiment 2), strip is monophasic Bi
2Te
3The type structure.
3) thin band material is milled be ground into powder, the compacting in the graphite jig of 15mm of packing into, put into discharge plasma sintering (SPS) stove together with graphite jig then and carry out sintering, sintering process is: under＜10Pa vacuum condition, heat-up rate is 100 ℃/min, sintering temperature is 500 ℃, and pressure is 20MPa, and sintering time is 5min; Sintering cools to room temperature with the furnace after finishing, and obtains the fine and close high performance and nano structure Bi with nanostructure
xSb
yTe
3-z(x=0.52, y=1.48,3-z=2.9～3.1) thermoelectric material sample (nanostructure size＜500nm, and it is nanocrystalline greater than 5% amorphous and 5～20nm to have a volume content).
To the high performance and nano structure Bi that obtains
xSb
yTe
3-zAfter polished finish is carried out on the surface of thermoelectric material sample, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.To the high performance and nano structure Bi that obtains
xSb
yTe
3-zRectangular parallelepiped and thickness that the thermoelectric material sample cuts into 2mm * 2mm * 8.0mm are the disk of 1.5mm, be used to measure Sai Beike (Seebeck) coefficient, specific conductivity and thermal conductivity, see Fig. 4 a, Fig. 4 b, Fig. 4 c, the ZT value of resulting sample reaches more than 1.2, and performance reaches 1.2～1.6 in the time of 60～100 ℃, shows that the technique means that provides by this invention can obtain the nanostructure Bi of thermoelectricity capability excellence
xSb
yTe
3-zThermoelectric material
Embodiment 3:
A kind of high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material is (to commercially available Bi
0.56Sb
1.42Te
3Carry out modification), it comprises the steps:
1) Bi for preparing with zone melting method
0.56Sb
1.42Te
3Alloy (commercially available) is an initial feed, takes by weighing 5g Bi
0.56Sb
1.42Te
3, put it in the steel die of 10mm and on tabletting machine, be pressed into block;
2) block that presses is packed in the quartz glass tube of single roller fast cooling device, under the argon gas atmosphere protection, earlier under high-frequency induction heating (electric current is that 8A, voltage are 200V) with the Bi in the quartz glass tube
0.56Sb
1.42Te
3Fusion obtains melt; In argon gas atmosphere, the argon gas spraying pressure is under the 4000r/min greater than the copper roller speed of rotation of 0.12MPa, single roller fast cooling device, and melt is got rid of tape handling, obtains having the Bi of nanostructure then
xSb
yTe
3-z(width is that 1～2mm, thickness are 15～20m) to (x=0.56, y=1.42 ,-z=2.85～3.15) thin band material; Shown in Fig. 1 (embodiment 3), strip is monophasic Bi
2Te
3The type structure.
3) thin band material is milled be ground into powder, the compacting in the graphite jig of 15mm of packing into, put into discharge plasma sintering (SPS) stove together with graphite jig then and carry out sintering, sintering process is: under＜10Pa vacuum condition, heat-up rate is 100 ℃/min, sintering temperature is 500 ℃, and pressure is 20MPa, and sintering time is 5min; Sintering cools to room temperature with the furnace after finishing, and obtains the fine and close high performance and nano structure Bi with nanostructure
xSb
yTe
3-z(x=0.56, y=1.42,3-z=2.85～3.15) thermoelectric material sample (nanostructure size＜500nm, and it is nanocrystalline greater than 5% amorphous and 5～20nm to have a volume content).
To the high performance and nano structure Bi that obtains
xSb
yTe
3-zAfter polished finish is carried out on the surface of thermoelectric material sample, carry out the thing identification of phases and microstructure analysis, and carry out the thermoelectricity capability test.To the high performance and nano structure Bi that obtains
xSb
yTe
3-zRectangular parallelepiped and thickness that the thermoelectric material sample cuts into 2mm * 2mm * 8.0mm are the disk of 1.5mm, be used to measure Sai Beike (Seebeck) coefficient, specific conductivity and thermal conductivity, see Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d has illustrated the composition that changes starting materials, the maximum thermoelectric figure of merit that has obtained material all can reach the level of 1.4-1.5, is higher than the thermoelectricity capability of the material of commercialization zone melting method preparation far away.
Fig. 2 A shows that the surface (abbreviating contact surface as) of thin band material (embodiment 2) the contact copper roller that obtains by the deepfreeze of single roller utmost point is very smooth, does not have into brilliant phenomenon, like non-crystalline state.Fig. 2 B is that the surface (abbreviating the free surface as) that thin band material does not contact the copper roller is the dendrite cross-like.The contrast of these two pictures as can be seen, the structure that obtains thin band material by the deepfreeze of single roller utmost point from contact surface like the dendrite transition of non-crystalline state to the free surface, huge variation has taken place in structure.Fig. 2 C has provided by strip and has obtained the profile scanning electromicroscopic photograph of block materials by the SPS sintering, shows not tangible orientation of the material grains that obtains, and does not have hole, the density height.Observed the fine microstructure of block behind strip and the SPS sintering by transmission electron microscope (TEM), the result is shown in Fig. 3 a and 3b, and Fig. 3 a is the TEM image of strip, as can be seen from the figure, comprising in the strip and be of a size of the nanocrystalline of 5-15nm, is the material of non-crystalline state around nanocrystalline.Strip is through behind the SPS sintering, and under nanostructure can be preserved in the SPS technology of design, Fig. 3 b had showed and also includes the meticulous nanocrystalline of 5-15nm in the SPS block materials.
The bound of x of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (2)
1. high performance and nano structure Bi
xSb
yTe
3-zThe preparation method of thermoelectric material is characterized in that it comprises the steps:
1) with commercially available Bi
2-xSb
xTe
3Be initial feed, wherein 0＜x＜2; On tabletting machine with Bi
2-xSb
xTe
3Be pressed into block;
2) with the Bi of block shape
2-xSb
xTe
3Pack in the quartz glass tube of single roller fast cooling device, under the argon gas atmosphere protection, earlier under high-frequency induction heating with the Bi in the quartz glass tube
2-xSb
xTe
3Fusion obtains melt; In argon gas atmosphere, the argon gas spraying pressure is under 500～5000r/min greater than the copper roller speed of rotation of 0.01MPa, single roller fast cooling device, and melt is got rid of tape handling, obtains thin band material then;
3) thin band material is milled be ground into powder, the compacting in the graphite jig of packing into, put into the discharge plasma sintering oven together with graphite jig then and carry out sintering, sintering process is: vacuum tightness remains on below the 10Pa, heat-up rate is 40～100 ℃/min, sintering temperature is 350～500 ℃, and pressure is 20～200MPa, and sintering time is 4～6min; Sintering cools to room temperature with the furnace after finishing, and obtains high performance and nano structure Bi
xSb
yTe
3-zThermoelectric material, 0＜x＜2 wherein, x+y=2 ,-0.2＜z＜0.2.
2. a kind of high performance and nano structure Bi according to claim 1
xSb
yTe
3-zThe preparation method of thermoelectric material is characterized in that: the electric current of described high-frequency induction heating is that 2～11A, voltage are 100～500V.
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|---|---|---|---|
| CNA2009100624235A CN101570321A (en) | 2009-06-04 | 2009-06-04 | Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100624235A CN101570321A (en) | 2009-06-04 | 2009-06-04 | Method for preparing BixSbyTe(3-z) thermoelectric material with high performance and nano structure |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734065A (en) * | 2019-03-14 | 2019-05-10 | 湖南大学 | A kind of nano porous metal compound-material, preparation method and application |
| CN112002796A (en) * | 2020-08-27 | 2020-11-27 | 武汉理工大学 | Rapid preparation of high-performance Bi easy to cut2Te3Method for producing thermoelectric material |
| CN113130908A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | Bismuth antimony telluride/graphene potassium ion battery cathode material with high-stability structure and preparation method thereof |
| CN113314660A (en) * | 2021-07-30 | 2021-08-27 | 深圳见炬科技有限公司 | Method for synthesizing porous thermoelectric material based on melting centrifugation and porous thermoelectric material |
| CN113774492A (en) * | 2021-09-13 | 2021-12-10 | 哈尔滨工业大学 | Preparation method of high-textured nanocrystalline bismuth telluride |
-
2009
- 2009-06-04 CN CNA2009100624235A patent/CN101570321A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734065A (en) * | 2019-03-14 | 2019-05-10 | 湖南大学 | A kind of nano porous metal compound-material, preparation method and application |
| CN112002796A (en) * | 2020-08-27 | 2020-11-27 | 武汉理工大学 | Rapid preparation of high-performance Bi easy to cut2Te3Method for producing thermoelectric material |
| CN112002796B (en) * | 2020-08-27 | 2021-09-07 | 武汉理工大学 | Rapid preparation of high-performance Bi easy to cut2Te3Method for producing thermoelectric material |
| CN113130908A (en) * | 2021-04-20 | 2021-07-16 | 安徽大学 | Bismuth antimony telluride/graphene potassium ion battery cathode material with high-stability structure and preparation method thereof |
| CN113314660A (en) * | 2021-07-30 | 2021-08-27 | 深圳见炬科技有限公司 | Method for synthesizing porous thermoelectric material based on melting centrifugation and porous thermoelectric material |
| CN113774492A (en) * | 2021-09-13 | 2021-12-10 | 哈尔滨工业大学 | Preparation method of high-textured nanocrystalline bismuth telluride |
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