CN1974079A - Process of preparing bismuth telluride-base thermoelectric material - Google Patents
Process of preparing bismuth telluride-base thermoelectric material Download PDFInfo
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- CN1974079A CN1974079A CNA2006101551134A CN200610155113A CN1974079A CN 1974079 A CN1974079 A CN 1974079A CN A2006101551134 A CNA2006101551134 A CN A2006101551134A CN 200610155113 A CN200610155113 A CN 200610155113A CN 1974079 A CN1974079 A CN 1974079A
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Abstract
The present invention discloses process of preparing bismuth telluride-base thermoelectric material. By means of controlling the technological parameters in mechanical alloying and SPS process to maintain the powder material size within certain range, and the fast densification of SPS technology to avoid the growth of crystal grain in the sintered block material, the present invention lowers the heat conductivity of the material while maintaining the electric performance unchanged basically, so as to improve the thermoelectric performance and mechanical performance, raise the utilization rate of the prepared material and improve the stability and reliability of the corresponding thermoelectric device. The bismuth telluride-base thermoelectric material preparing process combining mechanical alloying and SPS technology of the present invention is superior to available zone melting growth process, which is slow and needs precise control.
Description
Technical field
The present invention relates to thermoelectric material, specifically a kind of bismuth telluride (Bi that has good mechanical property and thermoelectricity capability simultaneously
2Te
3) preparation method of base thermoelectricity material.
Background technology
Thermoelectric conversion is that a kind of Seebeck effect of semi-conducting material and Pei Er of utilizing pastes effect realization heat energy and the direct technology of conversion mutually of electric energy, and two kinds of application forms of thermoelectric power generation and thermoelectric cooling are arranged; Its energy conversion efficiency depends primarily on the dimensionless performance index of material, i.e. ZT value (ZT=α
2σ T/ κ is that Seebeck coefficient, σ are that electrical conductivity, κ are that thermal conductivity, T are absolute temperature for α wherein).In the 50-60 age in 20th century, successively found the Bi of function admirable
2Te
3Sill, PbTe sill and SiGe alloy.Wherein, the performance figure of merit ZT of PbTe sill and SiGe alloy reaches peak value at middle gentle high-temperature area respectively, is often used as the thermoelectric power generation material; And Bi
2Te
3Base alloy material has good thermoelectricity capability near room temperature, its ZT value is about 1.0, still enjoys irreplaceable status in the thermoelectric cooling field at present.N type and P type bismuth telluride-base thermoelectric material can be prepared corresponding refrigeration device by flow deflector and ceramic substrate according to certain circuit design, it has unharmful substance and discharges, volume is little, movement-less part, can be in characteristics such as arbitrarily angled installation and operations, and adjustable size restraining speed of cooling and cryogenic temperature by operating current, be quick on the draw, the precision height, thereby in national defence, industry, fields such as medical treatment and daily life all obtain to use comparatively widely, as being used as electronic devices and components (Infrared Detectors, semiconductor laser, transistor, precision resistance components and parts etc.) low-temperature receiver, perhaps small-sized travelling refrigerator, household electrical appliance such as changes in temperature water dispenser.
Because bismuth telluride (Bi
2Te
3) belonging to trigonal system, its thermoelectricity capability has very strong anisotropy, has the maximum performance figure of merit on the direction that is parallel to basal plane (00l).Thereby common method such as zone-melting process or the Bridgman method that adopts crystal growth in commercially producing is to obtain to have the crystalline material of good thermoelectricity capability; But on the other hand, because the layered crystal structure of bismuth telluride causes its easy cleavage, extremely low, the poor processability of mechanical strength of the monocrystalline that obtains or polycrystalline material, this has not only had a strong impact on the reliability of stock utilization and components and parts, aggravated the short supply state of exotic materials such as current tellurium, bismuth, antimony, and further microminiaturization, variation and the high performance of components and parts have seriously been restricted, the bottleneck that becomes restriction thermoelectric cooling industry development and further develop high-end product.
Current, be to seek novel fabricating technology at the research emphasis of bismuth telluride-base thermoelectric material, so that it has high strength and high thermoelectricity capability simultaneously.The crystallization process that utilizes powder metallurgic method can avoid slowly and need accurately to control; avoided the volatilization problem of low melting point element such as Bi, Te under the molten condition; effectively eliminated existing component segregation phenomenon in the crystal growing process; with respect to growing by zone melting technology; less demanding, manufacturing cycle to equipment shorten, and finally can obtain evenly tiny microstructure, the good mechanical property of prepared material; be suitable for large-scale production, this preparation method has report more.After this adopt the prepared block materials of method such as hot pressing, hot extrusion, with respect to the molten crystal in district, because the grain refinement of material, mechanical property has raising by a relatively large margin; Yet also make thermoelectricity capability also not satisfactory simultaneously, its main cause is that the grain orientation degree is not high, but also exist other to remain the reason furtheing investigate and illustrate, for example need further to set forth because of chemical composition and microstructure took place in the preparation process variation influence to thermoelectricity capability; Theoretically, if take into full account the synergy of the two, make the part grain size between the mean free path of phonon and carrier, because the mean free path of carrier and low frequency long wave phonon is suitable, thereby can significantly reduce the lattice thermal conductivity of material and mobility of charge carrier is not had obvious influence, and then it is constant substantially to keep the overall thermal electrical property.
Discharge plasma sintering (SPS) is a kind of novel material preparation technology, and its main feature is to utilize pulse current directly heating and surface active, realizes the quick densifying sintering of material.Compare with traditional sintering method, can energy savings, improve device efficiency, reduce cost, the uniform crystal particles of sintered specimen, density height, mechanical property are good, have broad application prospects in field of material preparation.So far, existing multinomial SPS prepares the U.S. and the European patent (US005610366A of Skutterudite system thermoelectric material, US005929351A, EP0874406A3), utilize the quick densifying characteristics of SPS technology, the grain growth of thermoelectric material is inhibited, thereby thermal conductivity is reduced significantly and makes the ZT value obtain improving.The inventor once adopted and will distinguish molten crystal pulverizing, then in conjunction with discharge plasma sintering (SPS) technology, and the block materials that has obtained to have desirable mechanical property, and the molten crystal in the district of thermoelectricity capability and same composition suitable (ZL03150425.6).
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of new bismuth telluride-base thermoelectric material is provided.The present invention at first utilizes mechanical alloying method to prepare the bismuth telluride-base powder body material, utilizes discharge plasma sintering (SPS) technology to prepare corresponding block materials then, and purpose is to prepare the bismuth telluride (Bi that has good mechanical property and thermoelectricity capability simultaneously
2Te
3) base thermoelectricity material.By the every technological parameter in control mechanical alloying and the SPS process, the size of keeping powder body material is in the certain size scope, it is sub-micrometer scale, utilize the characteristics of SPS technology quick densifying, make the crystal grain of the sintering block materials phenomenon of not growing up, thereby keeping the thermal conductivity that reduces material on the basic basis of invariable of electric property, final thermoelectricity capability and the mechanical property of improving material simultaneously, and then the utilization rate that makes prepared material obtained to significantly improve, and greatly improves the stability and the reliability of thermo-electric device simultaneously.The present invention adopts mechanical alloying to prepare bismuth telluride-base thermoelectric material in conjunction with discharge plasma sintering technique, has omitted the slow and accurate growing by zone melting process of controlling of needs in commercially producing.
One of key problem in technology of the present invention is the preparation of powder body material, i.e. the technological parameter of mechanical alloying method control comprises ratio of grinding media to material, rotating speed and ball milling time etc., to obtain tiny and uniform powder body material.Two of key problem in technology is the optimization of sintering process parameter, the pattern of mainly comprise sintering temperature, exerting pressure and size, programming rate, temperature retention time etc.Following each step is specifically arranged:
1, the preparation of powder body material
At first according to corresponding stoicheiometry weighing element powder, the element powder formulation is a prior art.Then the element powder is placed the high-energy ball milling device, ratio of grinding media to material is 20: 1, and rotating speed is 200～1200 rev/mins; Every interval certain hour takes out a little with powder, utilizes X-ray diffraction to characterize its phase composition whether checking alloying, and utilizes SEM (SEM) that powder is carried out morphology observation.Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas, to avoid introducing problem of oxidation in the preparation process.
2, the preparation of block materials
This process needs to carry out in vacuum condition or inert atmosphere, can select graphite or special steel die for use.In preparation process, need strict control technological parameter, the pattern of mainly comprise sintering temperature, exerting pressure and size, programming rate, temperature retention time etc.Wherein, sintering temperature and heating rate are regulated by the size of pulse current.Sintering range is 300～550 ℃; The programming rate scope is 20～200 ℃/min; How many definite concrete temperature retention times according to material are generally 5～60min; Can take substep pressurization, in initial stage of sintering or disposable pressurization isotype of insulation initial stage, institute's applied pressure scope is 20～120MPa; Take the mode of recirculated water cooling to make sample be cooled near the taking-up of room temperature at last.
The sign of material mainly comprises every thermoelectricity capability parameter, bending strength and the device maximum temperature difference Δ T that obtain such as Seebeck coefficient α, conductivity, thermal conductivity κ
mMeasurement.Find that according to X-ray diffraction (XRD) and ESEM (SEM) utilize mechanical alloying method can obtain the bismuth telluride-base powder body material of complete alloying, its crystal grain is tiny evenly, as shown in Figure 1.The ZT value of agglomerated material is about 0.7～1.1; Utilize the maximum temperature difference Δ T of the prepared device of sintering block materials
mBe 60～67 ℃, and utilize the maximum temperature difference of the molten prepared device of crystal of respective area to be about 67 ℃.The bending strength of the molten crystal in district only is about 10MPa, and the significantly improving to the 100MPa of sintering block.
The P-type material that with the component is Bi-Sb-Te is an example, shown in Fig. 2～4: compare the quality factor α of agglomerated material with the molten crystal in district
2σ decreases, but thermal conductivity κ reduces significantly, finally is embodied in performance figure of merit ZT what for to being better than the molten crystalline material in corresponding district.
The invention provides a kind of bismuth telluride (Bi with excellent mechanical performances
2Te
3) base thermoelectricity material technology of preparing and technical process, microstructure by the control material, on the basis of maintaining heat electrical property, improve its mechanical property significantly, the stability of utilization rate, machinability and components and parts of material and reliability etc. all are greatly improved, the preparation process of this technology is simple, has a good application prospect.
Description of drawings
Fig. 1 is the X-ray diffractogram of sintering hot pressing block materials perpendicular to the surface of exerting pressure;
Fig. 2 is the molten crystal in the district of same composition and mechanical alloying in conjunction with the conductivity of the prepared block materials of SPS technology with measuring the variation of temperature graph of a relation;
Fig. 3 is the molten crystal in the district of same composition and mechanical alloying in conjunction with the thermal conductivity κ of the prepared block materials of SPS technology with measuring the variation of temperature graph of a relation;
Fig. 4 is the molten crystal in the district of same composition and mechanical alloying in conjunction with the performance figure of merit ZT of the prepared block materials of SPS technology with measuring the variation of temperature graph of a relation.
The specific embodiment
Below the present invention is described in further detail.
Embodiment 1: matrix component is the n type material of Bi-Te-Se
Weighing 21.15 gram Bi, 18.01 gram Te, 0.84 gram Se and 0.04 restrain BiCl at first respectively
3Four kinds of powders place the high-energy ball milling device then, and ratio of grinding media to material is 20: 1, and rotating speed is 800 rev/mins; The ball milling time is 24 hours.Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas, to avoid introducing problem of oxidation in the preparation process.
Then powder is packed into graphite jig and place the SPS burner hearth.Sintering process is carried out under vacuum condition, and the sintering temperature of employing is 400 ℃; Heating rate is 50 ℃/min; Temperature retention time is 4min; Adopt two step pressing mode, promptly institute's applied pressure is 30MPa before the sintering, and holding stage institute applied pressure is 60MPa; Take out sample near naturally cooling to room temperature at last.The bending strength of the block materials that obtains is 82MPa; Thermoelectricity capability figure of merit Z is 2.9 * 10
-3/ K.
Embodiment 2: matrix component is the P-type material of Bi-Sb-Te
Three kinds of powders such as weighing 6.01 gram Bi, 11.08 gram Sb and 24.12 gram Te place the high-energy ball milling device then at first respectively, and ratio of grinding media to material is 20: 1, and rotating speed is 600 rev/mins; The ball milling time is 30 hours.Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas, to avoid introducing problem of oxidation in the preparation process.
Then powder is packed into graphite jig and place the SPS burner hearth.Sintering process is carried out under vacuum condition, and the sintering temperature of employing is 360 ℃; Heating rate is 50 ℃/min; Temperature retention time is 2min; Adopt two step pressing mode, promptly institute's applied pressure is 30MPa before the sintering, and holding stage institute applied pressure is 60MPa; Take out sample near naturally cooling to room temperature at last.
The bending strength of the block materials that obtains is 73MPa; Thermoelectricity capability figure of merit Z is 3.3 * 10
-3/ K.The n type material that is obtained in P-type material that is obtained in this example and the example 1 combines refrigeration device, measures maximum temperature difference Δ T
mIt is 66 ℃.
Embodiment 3: initial particle size is less than the powder body material of 200nm
At first according to stoicheiometry weighing each element powder identical with embodiment 1, place the high-energy ball milling device then, ratio of grinding media to material is 20: 1, and rotating speed is 1000 rev/mins; The ball milling time is 20 hours.Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas, to avoid introducing problem of oxidation in the preparation process.
Then powder is packed into graphite jig and place the SPS burner hearth.Sintering process is carried out under vacuum condition, and the sintering temperature of employing is 320 ℃; Heating rate is 60 ℃/min; Temperature retention time is 2min; Adopt two step pressing mode, promptly institute's applied pressure is 20MPa before the sintering, and holding stage institute applied pressure is 40MPa; Take out sample near naturally cooling to room temperature at last.
The bending strength of the block materials that obtains is 91MPa; Thermoelectricity capability figure of merit Z is 3.0 * 10
-3/ K.Utilize the P type powder of same particle size distribution to be 82MPa in the bending strength of the following sintered body that obtains of identical process conditions; Thermoelectricity capability figure of merit Z is 3.4 * 10
-3/ K.Utilize the two to combine refrigeration device, measure maximum temperature difference Δ T
mIt is 67 ℃.
Embodiment 4: initial particle size is the powder body material of～20 μ m
At first according to stoicheiometry weighing each element powder identical with embodiment 1, place the high-energy ball milling device then, ratio of grinding media to material is 20: 1, and rotating speed is 800 rev/mins; The ball milling time is 48 hours.Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas, to avoid introducing problem of oxidation in the preparation process.
Then powder is packed into special steel molding jig and place the SPS burner hearth.Sintering process is carried out under vacuum condition, and the sintering temperature of employing is 400 ℃; Heating rate is 40 ℃/min; Temperature retention time is 5min; Adopt two step pressing mode, promptly institute's applied pressure is 30MPa before the sintering, and holding stage institute applied pressure is 60MPa; Take out sample near naturally cooling to room temperature at last.
With reference to accompanying drawing, Fig. 1 for the hot pressing block materials perpendicular to the surperficial X ray diffracting spectrum of exerting pressure: (a) the standard diffraction card of bismuth telluride: No.15-863; Mechanical alloying powder (b) 10 hours; (c) 20 hours; (d) 30 hours; (e) the mechanical alloying powder combines the block materials that is obtained with SPS; Fig. 2～4 are respectively the molten crystal in district of same composition and mechanical alloying and concern (sintering temperature: 360 ℃ in conjunction with electrical conductivity, thermal conductivity and the ZT value of the prepared block materials of SPS technology with measuring variation of temperature; Exert pressure: 60MPa; Temperature retention time: 5min).The bending strength of the block materials that obtains is 79MPa; Thermoelectricity capability figure of merit Z is 2.8 * 10
-3/ K.Utilize the P type powder of same particle size distribution to be 72MPa in the bending strength of the following sintered body that obtains of identical process conditions; Thermoelectricity capability figure of merit Z is 3.1 * 10
-3/ K.Utilize the two to combine refrigeration device, measure maximum temperature difference Δ T
mIt is 62 ℃.
Claims (2)
1, a kind of preparation technology of bismuth telluride-base thermoelectric material is characterized in that: bismuth telluride matrix component is Bi
2Te
3-Bi
2Se
3N type material or matrix component be Bi
2Te
3-Sb
2Te
3P-type material;
Preparation technology may further comprise the steps:
(1) preparation of powder body material
According to corresponding stoicheiometry weighing element powder, place the high-energy ball milling device then, ratio of grinding media to material is 20: 1, rotating speed is 200～1200 rev/mins; Every interval certain hour takes out a little with powder, utilizes X-ray diffraction to characterize its phase composition whether checking alloying, and utilizes SEM that powder is carried out morphology observation; Charging and get the material process and need in glove box, to carry out, and introduce inert gas shielding such as argon gas;
(2) preparation of block materials
In vacuum condition or inert atmosphere, with the powder of step (1) preparation pack into graphite jig or special steel die, and place discharge plasma sintering stove sintering, sintering range is 300～550 ℃; The programming rate scope is 20～200 ℃/min; Temperature retention time is 5～60min; Can take substep pressurization, in initial stage of sintering or disposable pressurization isotype of insulation initial stage, institute's applied pressure scope is 20～120MPa; Take the mode of recirculated water cooling to make sample be cooled near the taking-up of room temperature at last.
2, the preparation technology of bismuth telluride-base thermoelectric material according to claim 1 is characterized in that: described element powder is Bi, Te, Se, BiCl
3, Sb powder.
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| CN101786162B (en) * | 2010-01-19 | 2011-07-27 | 武汉科技大学 | Preparation method of bismuth telluride based bulk nano crystalline thermoelectric material |
| CN102154692A (en) * | 2011-02-25 | 2011-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method of In-Se-based thermoelectric material |
| CN101403139B (en) * | 2008-06-11 | 2012-08-08 | 中国科学院上海硅酸盐研究所 | Preparation method for bismuth telluride based sintered fuel |
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