CN1230377C - Method for preparing bismuth telluride base thermoelectric material - Google Patents
Method for preparing bismuth telluride base thermoelectric material Download PDFInfo
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- CN1230377C CN1230377C CN 03150425 CN03150425A CN1230377C CN 1230377 C CN1230377 C CN 1230377C CN 03150425 CN03150425 CN 03150425 CN 03150425 A CN03150425 A CN 03150425A CN 1230377 C CN1230377 C CN 1230377C
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Abstract
The present invention relates to a method for preparing bismuth telluride base thermoelectric materials, which is characterized in that bismuth telluride base oriented polycrystalline rods are prepared by using the zone-melting method, the melting temperature is 700 to 800 DEG C and the temperature gradient is 25DEG. C/mm; the polycrystalline rods are soaked in solutions of hydrofluoric acid in advance, and the rods are cleaned by using alcohol and deionized water after taken out until the pH of the surface is 7; the rods are dried in vacuum finally, then crushed and sieved, and ultrasonic wave pretreatment is carried out on powder lots before sintering; discharging plasma rapid sintering is carried out in vacuum or in inert atmosphere, the sintering temperature range is from 360 to 510 DEG C, the heating rate is 20 to 200 DEG C /mm, the sintering time is 10 to 60 min, and the pressure is 20 to 120MPa. On the basis of ensuring the thermoelectric conversion performance equal to zone-melting polycrystalline materials, the present invention causes utilization rate of materials, workability and product reliability to be greatly improved and production cost to be obviously reduced, and therefore, the present invention has a favorable prospect for industrial production.
Description
Technical field
The present invention relates to a kind of have high strength, high performance Tellurobismuthite (Bi
2Te
3) preparation method of base thermoelectricity material, belong to the thermoelectric material 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 of material, i.e. ZT value (Z=α
2σ/κ, wherein α is the Seebeck coefficient; σ is a specific conductivity; κ is a thermal conductivity).20th century 50 have been found refrigeration and electricity generation material that the thermo-electric conversion performance is higher, as Bi in succession to the sixties
2Te
3, solid solution alloies such as PbTe, SiGe.So far, Bi
2Te
3The base alloy is still near one of material that has best thermoelectric conversion performance room temperature, and its ZT value can reach about 1.0, and the occasion low at various refrigeration temperatures, that cooling load is less has wide application prospect.Influencing the maximum restraining factors that thermo-electric converting material uses is that its conversion efficiency of thermoelectric is low, but along with modern age technical applications constantly widen raising with level, the advantage of all kinds of thermo-electric devices that reach its maturity has been subjected to extensive concern.In today that environment protection comes into one's own day by day; thermo-electric device is free from environmental pollution because of it again, can utilize the potentiality of used heat and renewable energy source further to come into one's own, and is used widely at numerous areas such as petrochemical complex, detecting instrument, environmental protection, aerospace, health care, household electrical appliance.Especially be not to be the application scenario of major consideration with the effciency of energy transfer a lot, thermo-electric device has incomparable advantage, has movement-less part, noiseless, microminiaturization easily, is easy to characteristics such as control, reliability height, life-span length.
Bi
2Te
3Crystalline structure belong to R 3m trigonal system, can be considered the hexahedron laminate structure along crystalline C direction of principal axis.Its thermoelectricity capability is anisotropy, has the maximum performance figure of merit on the direction that is parallel to basal plane (00l).With Bi
2Te
3Be the formed Bi of matrix
2(Te, Se)
3(Bi, Sb)
2Te
3Sosoloid can constitute the N type and the P type galvanic couple arm of thermo-electric device respectively.At present, to Bi
2Te
3The research emphasis of base thermoelectricity material is to seek novel preparation technology.On principle, the figure of merit of monocrystal material is better than polycrystalline material, but because cleavage very easily, causes cracking in the body and makes its mis-behave.Usually adopt Bridgeman method or zone melting method to obtain to have the Bi of orientation
2Te
3Polycrystalline material, but in preparation process, be prone to segregation and cause the ZT value to reduce, and the sample that is obtained causes physical strength low along (00l) face cleavage easily, thus limited the processing and the work reliability of components and parts.Adopt machine-alloying can effectively eliminate the component segregation phenomenon, and avoided the volatilization problem of low melting point element such as Bi, Te under the molten state, finally obtain evenly tiny tissue.But it is comparatively serious to cause powder to pollute in the process of ball milling, and preparation cycle is long.In addition, adopt traditional sintering process, as hot pressing, hot extrusion etc., though the sample mechanical property that is obtained is made moderate progress, the grain orientation degree is high and make thermoelectricity capability lower.
Discharge plasma Fast Sintering (SPS) is a kind of novel material preparation technology, and its principal feature is to utilize pulsed current direct heating and surface active, realizes the quick densifying sintering of material.Compare with traditional sintering method, can save energy, improve plant 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 prepare U.S. of Skutterudite pyroelectric material and European patent (US005610366A, US005929351A, EP0874406A3).Utilize the quick densifying characteristics of SPS technology, the grain growing of this system thermoelectric material is inhibited, obtained higher specific conductivity keeping even reduce on the basis of thermal conductivity, thereby its performance figure of merit is improved.Skutterudite system thermoelectric material and Tellurobismuthite (Bi
2Te
3) difference of base thermoelectricity material maximum is that the former thermoelectricity capability is an isotropy, therefore do not need to consider the orientation of material in preparation process.In addition, people such as Kusano (Journal of the Japan Institute of Metals, Vol.66,2002,1063-1065) reported employing SPS technology, people such as Koyanagi (International Conference onThermoelectrics, ICT in conjunction with machine-alloying, 2001,278-281) reported and utilized SPS in-situ preparing Bi
2Te
3Base thermoelectricity material, but have shortcomings such as complex process or thermo-electric conversion performance be lower respectively.
Summary of the invention
The objective of the invention is to adopt discharge plasma Fast Sintering technology (SPS), the Tellurobismuthite (Bi that preparation has good mechanical property and thermo-electric conversion performance
2Te
3) base thermoelectricity material.
Key problem in technology of the present invention is to make crystal grain have good orientation within the specific limits, to obtain the sintered material with good mechanical property and thermo-electric conversion performance by process parameter optimizing, microstructure control.At first sieve the size-grade distribution of the initial powder of strict control by classification; In addition, the control sintering process parameter comprises sintering temperature, pressure, temperature rise rate, soaking time, applies the direction of electric field etc.Following each step is specifically arranged:
1. directed polycrystalline preparation
With element powders such as commercial Bi, Sb, Te, Se is raw material, utilizes zone melting method to prepare Tellurobismuthite (Bi
2Te
3) basic directed polycrystalline crystal bar.By adopting processing parameters such as rational temperature rise rate, melt temperature, thermograde, the speed of growth.Usually the temperature rise rate of taking is 25 ℃/min; Melt temperature is 700～800 ℃; Thermograde is 25 ℃/mm; The speed of growth is 25～30mm/h.According to different stoicheiometries, prepare N type Bi
2(Te, Se)
3With the P type (Bi, Sb)
2Te
3Thermoelectric material.
2. the preparation of powder and pre-treatment
The polycrystalline material that obtained is pulverized and sieved, make initial powder form different size-grade distribution.At first crystal bar being placed certain density hydrofluoric acid solution to soak, take out the back with alcohol and washed with de-ionized water, is about 7 until its surperficial pH value, carries out drying at last in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process can carry out in glove box, and introduces protection of inert gas such as argon gas.In atmosphere of inert gases, utilize the standard nylon sieve that powder is sieved, to form different size-grade distribution.Operate in air if pulverize, then need the powder after pulverizing, sieving is carried out aftertreatment, (Ar+5～40%H under reducing atmosphere with the process of sieving
2) be heated to about 300 ℃, and insulation was handled 4 hours under this temperature.Before sintering, powder is carried out ultrasonic pretreatment, make sintering powder in mould, form certain distribution of orientations.
3. discharge plasma Fast Sintering (SPS)
This process is carried out under vacuum condition or inert atmosphere, can select graphite or special steel die for use.In preparation process, need strict control process parameters, comprise sintering temperature, pressure, temperature rise rate, soaking time, apply the direction of electric field etc.Wherein, sintering temperature and temperature rise rate are regulated by the size of pulsed current and voltage.The agglomerating temperature range is 360～510 ℃; The temperature rise rate scope is 20～200 ℃/min; According to definite concrete sintering times such as the different initial particle size of powder, be generally 10～60min; Pressure range is 30～120Mpa, and it can once pressurize or adopt two step pressurizations at initial stage of sintering, applies a part of pressure before the sintering, and holding stage (being that sintering begins) applies a part of pressure again.
The performance evaluation of material mainly comprises the orientation analysis, the maximum temperature difference Δ T of bending strength, thermo-electric conversion performance (Seebeck factor alpha, conductivity, thermal conductivity κ) and the device that obtains
mMeasurement.Adopt above-mentioned preparation technology, the orientation factor F of the sintered material that is obtained is 0.3～0.9, as shown in Figure 1, 2.The result shows that after the SPS sintering, its crystal grain has good orientation.The performance figure of merit Z of each sample is 2.2～3.1 * 10
-3/ K; The maximum temperature difference Δ T of the device that obtains
mIt is 59～71 ℃.The bending strength of crystal bar only is about 10MPa, then the significantly improving to the 80MPa of sintered compact.
With the component is 93%Bi
2Te
3-7%Bi
2Se
3+ 0.13wt%TeI
4N type material be example, shown in Fig. 3,4: compare with the performance of crystal bar, through after the SPS sintering, its conductivity improves and thermal conductivity κ reduces, though the Seebeck factor alpha also decrease, the overall performance of the two, promptly Z value quite.
The invention provides a kind of Tellurobismuthite (Bi with good orientation and mechanical property
2Te
3) base thermoelectricity material and preparation technology thereof.By the quick densifying sintering with control microstructure, guaranteeing on the suitable basis of the molten directed polycrystalline material in thermo-electric conversion performance and district, utilization ratio, workability, the reliability of products of material are greatly improved, and production cost significantly reduces, thereby has good industrial prospect.
Description of drawings
Fig. 1 is an X-ray diffractogram (a.JCPD card; B. the sintered compact and the vertical surface of exerting pressure); Fig. 2 is the relation (pressure: 80MPa of orientation factor F and sintering temperature and initial particle size; Soaking time: 15min); Fig. 3 is that specific conductivity is with variation of temperature relation (pressure: 80MPa; Soaking time: 15min); Fig. 4 is that thermal conductivity is with variation of temperature relation (pressure: 80MPa; Soaking time: 15min).
Embodiment
Further set forth substantive distinguishing features of the present invention and obvious improvement below by embodiment.
Embodiment 1: initial particle size is the powder of 180～380 μ m
With the component is 93%Bi
2Te
3-7%Bi
2Se
3+ 0.15wt%TeI
4N type material be example, at first will distinguishing molten polycrystalline crystal bar, to place concentration be that 10～15% hydrofluoric acid solution soaks 30min, takes out the back with alcohol and washed with de-ionized water, and dry in a vacuum.Pulverize then and sieve, adopt Steel Vessel as the pulverizing instrument, crushing process utilizes protection of inert gas such as argon gas.Utilize the standard nylon sieve that powder is sieved, to obtain the initial powder that desired particle size distributes.Powder is packed into behind the mould, before sintering, carry out ultrasonic vibration and handle, to form certain distribution of orientations.
Utilize graphite jig, the SPS preparation process is carried out under vacuum condition.The sintering temperature that adopts is 460 ℃; Temperature rise rate is 80 ℃/min; Soaking time is 20min; Adopt two step pressing mode, institute's applied pressure is 40MPa before the sintering, and holding stage institute applied pressure is 80MPa.
The bending strength of the sintered compact that is obtained is 78MPa; Orientation factor F is 0.89; Thermoelectricity capability figure of merit Z is 2.78 * 10
-3/ K.
Embodiment 2: component is 20%Bi
2Te
3-80%Sb
2Te
3The P-type material of+3wt%Te
At first crystal bar being placed concentration is that 10～15% hydrofluoric acid solution soaks 20min, takes out the back with alcohol and washed with de-ionized water, and dry in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process adopts protection of inert gas such as argon gas.Utilize the standard nylon sieve that powder is sieved, make initial powder form different size-grade distribution.The powder of choosing 180～380 μ m is that raw material carries out the SPS sintering.Powder is packed into behind the mould, before sintering, carry out ultrasonic vibration and handle, to form certain distribution of orientations.
Utilize stainless steel mould, the SPS preparation process is carried out under vacuum condition.The sintering temperature that adopts is 440 ℃; Temperature rise rate is 80 ℃/min; Soaking time is 15min; Adopt two step pressing mode, institute's applied pressure is 30MPa before the sintering, and the holding stage applied pressure is 60MPa.
The bending strength of the sintered compact that is obtained is 83MPa; Orientation factor F is 0.81; Thermoelectricity capability figure of merit Z is 2.95 * 10
-3/ K.In this example in gained P-type material and the example 1 the gained n type material be assembled into refrigeration device, measure maximum temperature difference Δ T
mIt is 71 ℃.
Embodiment 3: initial particle size is the powder of 120～180 μ m
To the P type that obtained (Bi, Sb)
2Te
3The molten polycrystalline material in district is pulverized and is sieved.At first crystal bar being placed concentration is that 10～15% hydrofluoric acid solution soaks 20min, takes out the back with alcohol and washed with de-ionized water, and dry in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process carries out in air.Utilize the standard nylon sieve that powder is sieved, to obtain the initial powder that desired particle size distributes.Then powder is carried out aftertreatment, (Ar+20%H under reducing atmosphere
2) be heated to about 300 ℃, and be incubated 4 hours.Powder is packed into behind the mould, before sintering, carry out ultrasonic vibration and handle, to form certain distribution of orientations.
Utilize graphite jig, the SPS preparation process is carried out under vacuum condition.The sintering temperature that adopts is 420 ℃; Temperature rise rate is 50 ℃/min; Soaking time is 12min; At the disposable applied pressure of initial stage of sintering is 70MPa.
The bending strength of the sintered compact that is obtained is 82MPa; Orientation factor F is 0.75; Thermoelectricity capability figure of merit Z is 2.69 * 10
-3/ K.The N type powder of one-sizes such as utilization is 79MPa in the bending strength of the following sintered compact that obtains of identical processing condition; Orientation factor is 0.78; Thermoelectricity capability figure of merit Z is 2.76 * 10
-3/ K.Utilize the maximum temperature difference Δ T of the two assembling obtained device
mIt is 70 ℃.
Embodiment 4: initial particle size is the powder of 96～120 μ m
To the N type Bi that is obtained
2(Te, Se)
3The molten polycrystalline material in district is pulverized and is sieved.At first crystal bar being placed concentration is that 10～15% hydrofluoric acid solution soaks 20min, takes out the back with alcohol and washed with de-ionized water and dry in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process adopts protection of inert gas such as argon gas.Utilize the standard nylon sieve that powder is sieved, to obtain the initial powder that desired particle size distributes.
Utilize graphite jig, in the SPS preparation process, charge into rare gas elementes such as argon gas.The sintering temperature that adopts is 400 ℃; Temperature rise rate is 100 ℃/min; Soaking time is 8min; At the disposable applied pressure of initial stage of sintering is 60MPa.
The bending strength of the sintered compact that is obtained is 86MPa; Orientation factor F is 0.46; Thermoelectricity capability figure of merit Z is 2.28 * 10
-3/ K.The P type powder of one-sizes such as utilization is 82MPa in the bending strength of the following sintered compact that obtains of identical processing condition; Orientation factor is 0.49; Thermoelectricity capability figure of merit Z is 2.36 * 10
-3/ K.Utilize the maximum temperature difference Δ T of the two assembling obtained device
mIt is 65 ℃.
Claims (1)
1, a kind of preparation method of bismuth telluride-base thermoelectric material is characterized in that comprising following each step:
(1) utilize zone melting method to prepare the directed polycrystalline rod of bismuth telluride-base, melt temperature is 700-800 ℃, 25 ℃/mm of thermograde, and the speed of growth of polycrystalline rod is 25-30mm/h;
(2) earlier directed polycrystalline rod being placed concentration is that the hydrofluoric acid solution of 10-15% soaks, and takes out the back with alcohol and washed with de-ionized water, is 7 until surperficial PH; Dry in a vacuum at last; Polycrystalline rod adopts Steel Vessel then, pulverizes, sieves at argon gas or in air; Before the sintering powder is carried out ultrasonic pretreatment; If in air, pulverize and sieve operation, then need the powder after pulverizing, sieving is carried out aftertreatment, promptly containing 5～40%H
2Ar gas atmosphere under, the powder after pulverizing, sieving is heated to 300 ℃, insulation was handled 4 hours under this temperature;
(3) carry out the plasma discharging Fast Sintering under inert atmosphere, sintering range 360-510 ℃, temperature rise rate 20-200 ℃/min, sintering time 10-60min, pressure are 20-120Mpa;
The pressure that described sintering step adopts is to apply by such mode, adopts two step pressuring methods, applies a part of pressure before the sintering, and holding stage applies a part of pressure again; Or adopt pressuring method one time, promptly once exert pressure at initial stage of sintering;
Described bismuth telluride-base consists of N type Bi
2(Te, Se)
3Or the P type (Bi, Sb)
2Te
3
The sieve granularity of back powder of described powder is 180～380 μ m or 120～less than 180 μ m or 96～less than 120 μ m.
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