CN101435029A - Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material - Google Patents
Rapid preparation of high performance nanostructured filling type skutterudite thermoelectric material Download PDFInfo
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- CN101435029A CN101435029A CNA2008102374206A CN200810237420A CN101435029A CN 101435029 A CN101435029 A CN 101435029A CN A2008102374206 A CNA2008102374206 A CN A2008102374206A CN 200810237420 A CN200810237420 A CN 200810237420A CN 101435029 A CN101435029 A CN 101435029A
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Abstract
The invention relates to a preparing method of thermoelectric compound, in particular to a fast preparing method of filled type skutterudite thermoelectric material with high performance nanostructure. The invention is characterized in that the method comprises the following steps: 1) batching: granular Yb, granular Co and granular Sb are used as starting materials and weighed according to the chemical formula Yb0.3Co4Sb12.3; 2) preparing master alloy: the granular Yb, the granular Co and the granular Sb are mixed, then put into a melting furnace, heated slowly to 1100 DEG C by adopting rate of temperature increase of 2 DEG C/min and melted for 20 to 30h so as to obtain melt; the melt is quenched in supersaturated salt water so as to obtain the master alloy; 3) the master alloy is carried out cleaning processing, placed in an induction heating furnace to be melted to melt and then rotatablely throws the melt so as to obtain a strap product with an amorphous/nanocrystalline composite structure; and 4) the strap product with the amorphous/nanocrystalline composite structure is ground, tableted and then sintered by using discharging plasma so as to obtain filled type skutterudite thermoelectric material with high performance nanostructure. The method has short preparation period, low energy consumption, simple and easy-control technique, safety and no pollution.
Description
Technical field
The invention belongs to the new energy materials field, be specifically related to a kind of preparation method of thermoelectric compound.
Background technology
Thermo-electric generation is to utilize thermo-electric converting material heat energy to be converted into the complete static direct generation of electricity mode of electric energy, advantages such as flexible are leaked, moved to noiseless, nothing wearing and tearing, nothing when having compact equipment, dependable performance, operation, can produce electromotive force under the situation that has small temperature difference to exist, has important effect at military affairs, space flight, medical science, microelectronic, along with becoming increasingly conspicuous of energy and environment problem, thermoelectric cell has attracted increasing concern as wide accommodation and the green energy resource technology that meets environmental protection.
Filled skutterudite (skutterudite) compound shows the thermoelectric transport property of electron crystal-phonon glass, especially rich Co forms and has bigger Seebeck coefficient and high melt point and high-temperature stability preferably, therefore causes people's very big interest as warm electric material in a kind of performance index with potential high heat novel.Filling type skutterudite compound is to add the compound that fills atoms metal in the icosahedron cavity formed of the Sb atom in the skutterudite structure, this compounds not only has big current carrier degree of excursion, high specific conductivity and bigger Seebeck coefficient, strengthen the scattering process of phonon simultaneously owing to the disturbance of the atom in the icosahedron cavity that is filled in Sb, lattice thermal conductivity is reduced, thereby be expected to obtain having high-performance exponential thermoelectric material.Many in addition studies show that, macro-scale is at the thermoelectric material of nanoscale, its performance index is compared with corresponding block thermoelectric material and is greatly improved, quantum confinement effect after the material low-dimensionalization can cause near the density of electronic states increase the material fermi level that material Seebeck coefficient is increased, simultaneously a large amount of crystal boundary scattering significantly reduces the thermal conductivity of material to the scattering of phonon in the material, and the acting in conjunction of two aspects significantly increases material ZT value.At present, for CoSb
3The preparation method of polycrystalline compounds have solid reaction process (Solid state reaction, SSR), coprecipitation method (Cross-Coprecipitation, CC), sol-gel method (Sol-Gel method, SG) etc.Tradition SSR method preparation cycle is long, generally needs 7～10 days, and the consumption of time, the energy was not being had than quantum jump in recent years than big and performance.Other chemical method such as CC and SG method, though can obtain the tiny nano-powder of grain-size, but because the surface oxidation of nano particle and the existence of a large amount of bulk defectss, its sintering densification process is brought disadvantageous effect, often density is not high to cause final agglomerating block product, and thermoelectricity capability is undesirable.
Summary of the invention
The object of the present invention is to provide a kind of fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material, this method preparation cycle is short, energy consumption is low, technology is simple.
To achieve these goals, technical scheme of the present invention is: the fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material is characterized in that it comprises the steps:
1) batching: with granular Yb, granular Co and granular Sb is starting raw material, presses chemical formula Yb
0.3Co
4Sb
12.3Weigh; Wherein, the purity of granular Yb 〉=99.98% (quality), the purity of granular Co 〉=99.99% (quality), the purity of granular Sb 〉=99.9999% (quality);
2) preparation of mother alloy: granular Yb, granular Co and granular Sb are mixed, put into melting furnace then, adopt the heat-up rate of 2 ℃/min slowly to be heated to 1100 ℃, fusion 20～30h gets melt; Melt is quenched in supersaturated brine, obtain mother alloy (compact metal glossy ingot body);
3) mother alloy is carried out clean, place induction heater to be smelted into melt, melt is revolved get rid of then, get the strand of product of amorphous/nanocrystalline composite structure;
4) strand of product of amorphous/nanocrystalline composite structure being ground, behind the compressing tablet, use discharge plasma sintering, must high performance nanostructured filling type skutterudite thermoelectric material (be Yb
0.3Co
4Sb
12.3The thermoelectric compound block materials).
Step 3) is described carries out clean with mother alloy and is: the mother alloy that obtains use the ethanol ultrasonic cleaning after surface contaminants and impurity are removed in sand papering, drying, the mother alloy after must clean; The described melt that is smelted into is: the mother alloy after the clean is put into the bottom to be had the quartz glass tube of a diameter 0.35mm circular hole and places the induction melting furnace melting, is evacuated to 5 * 10 earlier in the stove
-3Pa fills with the high-purity argon gas protection again, and the purity of high-purity argon gas 〉=99.99% gets melt; Described with melt revolve get rid of for: it is the copper roller surface of 30m/s high speed rotating that melt is ejected under the whiff pressure of 0.02MPa with the linear velocity, obtains thickness 8～10 μ m, the amorphous strand of product of wide 1～1.5mm.
The described of step 4) with discharge plasma sintering is: with discharge plasma sintering method sintering under vacuum, sintering temperature is 550 ℃, time is 5min, obtain single-phase, relative density greater than 98%, average grain size is about the n type Yb of 250nm, thermoelectricity capability index ZT up 1.3
0.3Co
4Sb
12.3The thermoelectric compound block materials.
The invention has the beneficial effects as follows: it is mother alloy that the present invention adopts the ingot body after the direct fusion of simple substance element-quenching, more traditional fusion-the diffusion annealing of its preparation cycle-sintering densification method ratio, shortened in 40 hours from 7～10 days, a large amount of annealing times (having saved the annealing time more than 100 hours in the traditional technology) have been saved, it is about 80% that the material preparation cycle has been shortened than prior synthesizing method, greatly reduces preparation cost and obtained high thermoelectricity capability.Melt revolves and gets rid of technology and discharge plasma sintering reaction heat treatment control of process parameters and optimize also extremely important in addition, the present invention adopts melt to revolve to get rid of technology each composition in the mother alloy further is evenly distributed, and the amorphous that obtains, nanocrystalline structure help forming the uniform tin white cobalt phase of nanocrystalline grain size fast in discharge plasma sintering process thereafter, and realize densification.The present invention has that technology is simple and easy to control, the reaction times is short, energy consumption is low, safety non-pollution, good reproducibility, obtain characteristics such as block materials thermoelectricity capability height.The n type Yb that obtains
0.3Co
4Sb
12.3Compound block materials microcosmic grain-size is 250nm, and according to concrete test parameter difference, grain-size is adjustable.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the XRD figure spectrum of strand of product in the embodiment of the invention 1.
Fig. 3 (a) is the field emission scanning electron microscope photo (FESEM) on the free surface of strand of product in the embodiment of the invention 1.
Fig. 3 (b) is the field emission scanning electron microscope photo (FESEM) of the contact surface of strand of product in the embodiment of the invention 1.
Fig. 4 is Yb in the embodiment of the invention 1
0.3Co
4Sb
12.3The XRD figure spectrum of thermoelectric compound block materials.
Fig. 5 is Yb in the embodiment of the invention 1
0.3Co
4Sb
12.3The field emission scanning electron microscope photo (FESEM) of thermoelectric compound block materials.
Fig. 6 is Yb in the embodiment of the invention 1
0.3Co
4Sb
12.3The thermoelectricity capability figure of thermoelectric compound block materials.
Specific implementation method
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to the following examples below in conjunction with embodiment.
Embodiment 1:
As shown in Figure 1, the fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material, it comprises the steps:
1) batching: with granular Yb, granular Co and granular Sb is starting raw material, and reaction raw materials is pressed chemical formula Yb
0.3Co
4Sb
12.3Weigh; Wherein, the purity of granular Yb is 99.98% (quality), and the purity of granular Co is 99.99% (quality), and the purity of granular Sb is 99.9999% (quality);
2) preparation of mother alloy: granular Yb, granular Co and granular Sb are mixed, put into melting furnace then, adopt the heat-up rate of 2 ℃/min slowly to be heated to 1100 ℃, fusion 20～30h (has in this scope and can realize the present invention, as 20h or 30h), get melt; Melt is quenched in supersaturated brine, obtain mother alloy (compact metal glossy ingot body);
3) preparation of strand of product: the mother alloy that obtains is used the ethanol ultrasonic cleaning after surface contaminants and impurity are removed in sand papering, putting into the bottom after the drying has the quartz glass tube of a diameter 0.35mm circular hole and places the induction melting furnace melting, is evacuated to 5 * 10 earlier in the stove
-3Pa fills with high-purity argon gas protection, the purity of high-purity argon gas 〉=99.99% again; It is the copper roller surface of 30m/s high speed rotating that melt is ejected under the whiff pressure of 0.02MPa with the linear velocity, obtains thickness 8～10 μ m, the strand of product of the amorphous/nanocrystalline composite structure of wide 1～1.5mm; The XRD figure of the strand of product of amorphous/nanocrystalline composite structure spectrum is seen Fig. 2, the relative broadening of the diffraction peak of strand of product as seen from Figure 2, product component complexity; The field emission scanning electron microscope photo of strand of product is seen Fig. 3 (a), Fig. 3 (b), by Fig. 3 (a) as seen, and the free surface of strand of product (with the one side that the copper roller directly contacts, another side is the free surface) the about 20nm of average grain size; By Fig. 3 (b) as seen, the contact surface of strand of product does not have micro-details, similar amorphous;
4) strand of product of amorphous/nanocrystalline composite structure is ground, behind the compressing tablet, with discharge plasma sintering method sintering under vacuum, sintering temperature is 550 ℃, time is 5min, obtain single-phase, relative density greater than 98%, average grain size is about the n type Yb of 250nm, thermoelectricity capability index ZT up 1.3
0.3Co
4Sb
12.3Thermoelectric compound block materials (being high performance nanostructured filling type skutterudite thermoelectric material).Yb
0.3Co
4Sb
12.3The XRD figure spectrum of thermoelectric compound block materials is seen Fig. 4, and as shown in Figure 4, strand of product has obtained single-phase filled skutterudite compound behind discharge plasma sintering; Yb
0.3Co
4Sb
12.3The field emission scanning electron microscope photo of thermoelectric compound block materials is seen Fig. 5, as shown in Figure 5, and Yb
0.3Co
4Sb
12.3The thermoelectric compound block materials is made up of the even grained of grain-size about 250nm; Yb
0.3Co
4Sb
12.3The thermoelectricity capability of thermoelectric compound block materials (characterizing with the ZT value) is seen Fig. 6, as seen from the figure the Yb of this experimental technique preparation
0.3Co
4Sb
12.3Thermoelectric material has very high thermoelectricity capability, and its ZT value reaches 1.3 in the time of 530 ℃.
Claims (3)
1. the fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material is characterized in that it comprises the steps:
1) batching: with granular Yb, granular Co and granular Sb is starting raw material, presses chemical formula Yb
0.3Co
4Sb
12.3Weigh; Wherein, the purity of granular Yb 〉=99.98%, the purity of granular Co 〉=99.99%, the purity of granular Sb 〉=99.9999%;
2) preparation of mother alloy: granular Yb, granular Co and granular Sb are mixed, put into melting furnace then, adopt the heat-up rate of 2 ℃/min slowly to be heated to 1100 ℃, fusion 20～30h gets melt; Melt is quenched in supersaturated brine, obtain mother alloy;
3) mother alloy is carried out clean, place induction heater to be smelted into melt, melt is revolved get rid of then, get the strand of product of amorphous/nanocrystalline composite structure;
4) strand of product of amorphous/nanocrystalline composite structure ground, behind the compressing tablet, use discharge plasma sintering, must high performance nanostructured filling type skutterudite thermoelectric material.
2. the fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material according to claim 1, it is characterized in that: step 3) is described carries out clean with mother alloy and is: the mother alloy that obtains is used the ethanol ultrasonic cleaning after surface contaminants and impurity are removed in sand papering, drying, the mother alloy after the clean; The described melt that is smelted into is: the mother alloy after the clean is put into the bottom to be had the quartz glass tube of a diameter 0.35mm circular hole and places the induction melting furnace melting, is evacuated to 5 * 10 earlier in the stove
-3Pa fills with the high-purity argon gas protection again, and the purity of high-purity argon gas 〉=99.99% gets melt; Described with melt revolve get rid of for: it is the copper roller surface of 30m/s high speed rotating that melt is ejected under the whiff pressure of 0.02MPa with the linear velocity.
3. the fast preparation method of high performance nanostructured filling type skutterudite thermoelectric material according to claim 1, it is characterized in that: the described of step 4) with discharge plasma sintering is: with discharge plasma sintering method sintering under vacuum, sintering temperature is 550 ℃, and the time is 5min.
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| CN101857929A (en) * | 2010-04-06 | 2010-10-13 | 武汉理工大学 | Zinc antimony based porous p-type thermoelectric material and preparation method thereof |
| CN101694010B (en) * | 2009-09-29 | 2012-01-11 | 武汉理工大学 | Preparation method of layered nanostructured InSb pyroelectric material |
| CN104022218A (en) * | 2014-06-23 | 2014-09-03 | 武汉理工大学 | High-performance SbAgSeS-based thermoelectric material and preparation method thereof |
| CN106159077A (en) * | 2015-03-30 | 2016-11-23 | 武汉理工大学 | A kind of bismuth telluride-based thermoelectric generating element and preparation method thereof |
| CN106191522A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of laser efficiently prepares the method for skutterudite thermoelectric material |
| CN107293637A (en) * | 2016-03-30 | 2017-10-24 | 武汉理工大学 | A kind of preparation method of high-performance GeSbTe base thermoelectricity materials |
| CN109022863A (en) * | 2018-07-16 | 2018-12-18 | 电子科技大学 | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga |
| CN110317971A (en) * | 2019-07-08 | 2019-10-11 | 哈尔滨工业大学 | A method of collaboration improves skutterudite thermoelectric material thermoelectricity capability and mechanical performance |
| CN114082968A (en) * | 2021-10-26 | 2022-02-25 | 广州大学 | Method for large-scale preparation of filled skutterudite material by spray rotary quenching |
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2008
- 2008-12-26 CN CNA2008102374206A patent/CN101435029A/en active Pending
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| CN101694010B (en) * | 2009-09-29 | 2012-01-11 | 武汉理工大学 | Preparation method of layered nanostructured InSb pyroelectric material |
| CN101857929A (en) * | 2010-04-06 | 2010-10-13 | 武汉理工大学 | Zinc antimony based porous p-type thermoelectric material and preparation method thereof |
| CN104022218A (en) * | 2014-06-23 | 2014-09-03 | 武汉理工大学 | High-performance SbAgSeS-based thermoelectric material and preparation method thereof |
| CN106159077A (en) * | 2015-03-30 | 2016-11-23 | 武汉理工大学 | A kind of bismuth telluride-based thermoelectric generating element and preparation method thereof |
| CN107293637B (en) * | 2016-03-30 | 2020-04-21 | 武汉理工大学 | Preparation method of high-performance GeSbTe-based thermoelectric material |
| CN107293637A (en) * | 2016-03-30 | 2017-10-24 | 武汉理工大学 | A kind of preparation method of high-performance GeSbTe base thermoelectricity materials |
| CN106191522A (en) * | 2016-07-12 | 2016-12-07 | 中国科学院上海硅酸盐研究所 | A kind of laser efficiently prepares the method for skutterudite thermoelectric material |
| CN109022863A (en) * | 2018-07-16 | 2018-12-18 | 电子科技大学 | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga |
| CN109022863B (en) * | 2018-07-16 | 2020-09-25 | 电子科技大学 | Ga-filled skutterudite thermoelectric material and preparation method thereof |
| CN110317971A (en) * | 2019-07-08 | 2019-10-11 | 哈尔滨工业大学 | A method of collaboration improves skutterudite thermoelectric material thermoelectricity capability and mechanical performance |
| CN110317971B (en) * | 2019-07-08 | 2020-12-29 | 哈尔滨工业大学 | Method for synergistically improving thermoelectric performance and mechanical performance of skutterudite thermoelectric material |
| CN114082968A (en) * | 2021-10-26 | 2022-02-25 | 广州大学 | Method for large-scale preparation of filled skutterudite material by spray rotary quenching |
| CN114082968B (en) * | 2021-10-26 | 2023-08-29 | 广州大学 | Method for preparing filled skutterudite material in large scale by spray spin quenching |
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Open date: 20090520 |