CN105420529A - Ultrafast synthetic method of Ag2X block thermoelectric material - Google Patents

Ultrafast synthetic method of Ag2X block thermoelectric material Download PDF

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Publication number
CN105420529A
CN105420529A CN201510747203.1A CN201510747203A CN105420529A CN 105420529 A CN105420529 A CN 105420529A CN 201510747203 A CN201510747203 A CN 201510747203A CN 105420529 A CN105420529 A CN 105420529A
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thermoelectric material
synthetic method
block thermoelectric
block
ultrafast
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CN105420529B (en
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唐新峰
杨东旺
付婕妃
苏贤礼
鄢永高
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Abstract

The invention discloses an ultrafast synthetic method of a Ag2X block thermoelectric material. The ultrafast synthetic method is characterized in that Ag and an X elementary substance are taken as raw materials, high pressure is applied at the normal temperature after the raw materials are mixed uniformly, the mixed materials react and are densified by one step, and the Ag2X block thermoelectric material is prepared, wherein X is Se or Te. The densities of Ag2Se and Ag2Te blocks prepared by the ultrafast synthetic method are above 97%; the relevant preparation time is short, and a technology is simple; in addition, the problem of element volatilization in high-temperature synthetic processes of selenide and telluride is solved; accurate control on components and a microstructure is realized; the thermoelectric properties of obtained products are superior to those of products prepared by the traditional preparation method; ZTmax of obtained Ag2Se is equal to 0.65@107 DEG; ZTmax of obtained Ag2Te is equal to 0.7@127 DEG; and the ultrafast synthetic method lays a good foundation for large-scale preparation and large-scale application of Ag2Seand Ag2Te thermoelectric materials.

Description

A kind of Ag 2the supper-fast synthetic method of X block thermoelectric material
Technical field
The invention belongs to thermoelectric material preparing technical field, be specifically related to a kind of Ag 2the supper-fast synthetic method of X block thermoelectric material.
Background technology
In recent ten years, the energy and environmental problem highlight gradually, and energy dilemma and ecocrisis cause concern day by day.At present, about have 70% to be wasted with the form of used heat in the annual energy consumed in the whole world, if these used heat effectively can be recycled, energy starved problem will be alleviated greatly.Thermal power transfer directly can be become electric energy by thermoelectric material, has the advantages such as, noiselessness little without drive disk assembly, volume, pollution-free, good reliability, recycles in automobile waste heat, has huge application prospect in industrial afterheat power generation.The efficiency of conversion of thermoelectric material determines (ZT=α by zero dimension thermoelectric figure of merit ZT 2σ T '/κ, wherein α is Seebeck coefficient, σ is specific conductivity, κ is thermal conductivity, Τ is absolute temperature).ZT is larger, and the conversion efficiency of thermoelectric of material is higher.
Compd A g 2se, Ag 2te occupies critical role at heat-electric energy conversion art, because it is excellent thermoelectric material.At present, compd A g 2se, Ag 2the synthetic method of Te mainly concentrates on hydrothermal method, solvent-thermal method etc., and these prepare Ag in the solution 2se, Ag 2the method of Te, often needs complicated reaction process and strict reaction conditions.More regrettably, the chemical reagent using some poisonous is needed, time consumption and energy consumption, contaminate environment.And adopt the preparation of conventional long high-temperature melting method, high-temperature solid phase reaction method, then harsh to equipment requirements, consume energy simultaneously, easily cause the disappearance of Se or Te, be difficult to accurate control composition.Therefore, seek a kind of normal temperature, Simple energy-saving, environmental protection, can the Ag of accurately control composition and microstructure 2se, Ag 2te preparation and quick densifying technology seem extremely urgent.
Summary of the invention
The object of this invention is to provide a kind of Ag 2the synthetic method of X block thermoelectric material, its preparation technology is simple, quick, and accurately can control product component, environmental protection, suitability for scale production.
For achieving the above object, the technical solution used in the present invention is: a kind of Ag 2the synthetic method of X block thermoelectric material, mixing raw material, is suppressed after mixing for raw material with Ag and X simple substance by it under normal temperature condition under pressure field effect, and the reaction of pressing process Raw and densification process one step of product complete, obtained fine and close Ag 2x block thermoelectric material, wherein X is Se or Te.
In such scheme, described simple substance Ag and X is with (1.8 ~ 2): the mol ratio of (1 ~ 1.1) accurately controls.
In such scheme, described pressing process is: pressurize 1 ~ 5min under 2 ~ 5GPa.
Preferably, described pressing process is: pressurize 1 ~ 5min under 2.5 ~ 3.5GPa.
In such scheme, described mixing raw material can carry out precompressed before applying pressure, and pre-compaction process is: pressurize 5 ~ 20min under 5 ~ 10MPa.
Fine and close Ag can be obtained in 15min according to such scheme 2x block thermoelectric material (X is Se or Te), the Ag of preparation 2se, Ag 2te block density, all more than 97%, can realize the densification levels of conventional high temperature densification technology (as SPS, PAS etc.), and effectively can avoid the Ag that heat treatment process thermograde is brought +transport phenomena, promotes Ag 2the application of X compound in thermoelectric material field.
The Ag obtained according to such scheme 2x block thermoelectric material, under 107 DEG C of temperature condition, Ag 2the thermoelectric figure of merit ZT of Se block thermoelectric material max=0.65; Ag under 127 DEG C of temperature condition 2the thermoelectric figure of merit ZT of Te block thermoelectric material max=0.7.
By the Ag prepared according to such scheme 2se block thermoelectric material is vacuum-sealed in quartz glass tube, and be placed in retort furnace be heated to 250 ~ 350 DEG C annealing 1.5 ~ 2.5h, must anneal Ag 2se block thermoelectric material.Thermoelectricity capability test result shows, under 116 DEG C of temperature condition, and its thermoelectricity capability ZT max=1.1, far above the block materials of the preparations such as room temperature high-pressure method, melting-pressure sintering, melting-SPS method, melting-PAS method, dynamically/static load-SPS method.
Based on foregoing, under the prerequisite not departing from basic fundamental thought of the present invention, according to ordinary technical knowledge and the means of this area, the amendment of various ways, replacement or change can also be had to its content.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention makes public for the first time a kind of Ag 2the supper-fast synthetic method of X block thermoelectric material, whole preparation process completes in several minutes, simultaneously simple, the environmental protection of preparation technology, suitability for scale production.
2) in the present invention be one supper-fast preparation Ag under pressure field 2the method of X block thermoelectric material, synthesis and the densification of material is realized at room temperature condition and high-pressure field action one step, thoroughly solve the volatilization problems of selenide and telluride Se and Te element in high-temperature process, achieve the accurate control of composition and microstructure, be conducive to improving Ag 2the thermoelectricity capability of X.
3) the present invention can effectively at Ag 2phase transition temperature (the Ag of X compound 2se corresponds to 134 DEG C, Ag 2te corresponds to 147 DEG C) following synthetic materials (room temperature), and the Ag that high-temperature heat treatment process thermograde brings can be avoided +migration problem, can accurate control composition, is all significant at material preparation science and commercial applications field.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of embodiment 1 products therefrom.
Fig. 2 is the FESEM photo of embodiment 1 products therefrom section.
Fig. 3 is the back scattering photo of embodiment 1 products therefrom polished surface.
Fig. 4 is that the thermal diffusivity of embodiment 1 products therefrom and thermal conductivity vary with temperature curve.
Fig. 5 is that the power factor of embodiment 1 products therefrom and zero dimension thermoelectric figure of merit ZT vary with temperature curve.
Fig. 6 is that embodiment products therefrom is through annealing heat treatment process gained annealing Ag 2power factor and the zero dimension thermoelectric figure of merit ZT of Se block thermoelectric material vary with temperature curve.
Fig. 7 is the XRD figure spectrum of embodiment 2 products therefrom.
Fig. 8 is the FESEM photo of embodiment 2 products therefrom section.
Fig. 9 is the back scattering photo of embodiment 2 products therefrom polished surface.
Figure 10 is that the thermal diffusivity of embodiment 2 products therefrom and thermal conductivity vary with temperature curve.
Figure 11 is that the power factor of embodiment 2 products therefrom and thermoelectric figure of merit ZT vary with temperature curve.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with drawings and Examples, but content of the present invention is not only confined to the following examples.
In following examples, the Ag powder of employing, Se powder and Te powder are commercially available prod, and purity is 5N.
Embodiment 1
A kind of Ag 2the supper-fast synthetic method of Se block thermoelectric material, concrete steps are as follows:
1) Ag powder and Se powder are undertaken weighing common 5g by the mol ratio of 2:1, after medication spoon mix 7min, gained mixing raw material is loaded in the stainless steel mould of Φ 15mm, afterwards this mould is put into the manual powder compressing machine of 769YP-24B (24T) and carry out precompressed (under 5MPa pressurize 10min), the demoulding obtains pressed compact;
2) get each one of size molybdenum matter " cup " the shape container (mug can be fastened on cuvette, plays sealing function) that matching size closes, pressed compact is loaded in little " cup ", then buckle large " cup ";
3) by step 2) in loaded pressed compact molybdenum matter " cup " shape groups of containers install in agalmatolite transmission medium;
4) by step 3) the agalmatolite assembly that obtains is placed in the CS-IIID artificial diamond hydraulic machine (the large press of cubic apparatus) that Guilin Metallurgy Machinery Principal Station manufactures and suppresses, the oil pressure of pressing process is that 40MPa (shows the pressure calibration of press cavity, the pressure at about 13MPa oil pressure respective chamber center is 1GPa), the pressure at respective chamber center is 3GPa, and the dwell time is 3min;
5) take out the complete block sample of compacting after release, obtain described Ag 2se block thermoelectric material.
Fig. 1 is the XRD figure spectrum of the present embodiment products therefrom, and showing products therefrom in figure is good Ag 2se is single-phase, and under room temperature condition is described, imposing 3GPa high pressure to Ag powder and Se powder can synthesize Ag in 3min 2se compound.Utilize Archimedes method to test product density to find, its density is 97.9%, and this high-pressure method technology of preparing is not only supper-fast as seen obtains target compound, and a step achieves densification simultaneously.Microscopic appearance sign is carried out to products therefrom section, the results are shown in Figure in 2, figure and show grain-size and be 50-100nm, these nanocrystalline can effective scattering phonon, reduce the thermal conductivity of products therefrom, be conducive to the thermoelectricity capability improving product.Electronic probe microcell back scattering observation will be carried out as shown in Figure 3 after its surface polishing, contrast consistent (cracks influence that removing surface finish brings), show product chemistry distributed components, do not have obvious second-phase to produce, prove the validity of present method further.Fig. 4 is that product thermal diffusivity and thermal conductivity vary with temperature curve, because exist near 107 DEG C phase transformation (may due to the impact of fine nanostructur make that its transformation temperature will be low relative to 134 DEG C of large grain size many), so there is extreme point on curve.Fig. 5 is that product power factor and zero dimension thermoelectric figure of merit ZT vary with temperature curve, 107 DEG C time, and ZT max=0.65.
The present embodiment products therefrom is vacuum-sealed in the quartz glass tube of Φ 20, and be placed in retort furnace be heated to 300 DEG C annealing 2h, must anneal Ag 2se block thermoelectric material.Fig. 6 is gained annealing Ag 2power factor and the zero dimension thermoelectric figure of merit ZT of Se block thermoelectric material vary with temperature curve, 116 DEG C time, and ZT max=1.1, far above the block materials of the preparations such as room temperature high-pressure method, melting-pressure sintering, melting-SPS method, melting-PAS method, dynamically/static load-SPS method.The volatilization problems of the Se element that further proof technical scheme of the present invention can effectively avoid selenide easily to produce in high temperature preparation process, and the Ag that can avoid that high-temperature process thermograde brings +migration problem, can accurate control composition, effectively improves Ag 2the thermoelectricity capability of Se.
Embodiment 2
A kind of Ag 2the supper-fast synthetic method of Te block thermoelectric material, concrete steps are as follows:
1) Ag powder and Te powder are undertaken weighing common 5g by the mol ratio of 2:1, after medication spoon mix 7min, gained mixing raw material is loaded in the stainless steel mould of Φ 15mm, afterwards this mould is put into the manual powder compressing machine of 769YP-24B (24T) and carry out precompressed (under 10MPa pressurize 5min), the demoulding obtains pressed compact;
2) get each one of size molybdenum matter " cup " the shape container (mug can be fastened on cuvette, plays sealing function) that matching size closes, pressed compact is loaded in little " cup ", then buckle large " cup ";
3) by step 2) in loaded pressed compact molybdenum matter " cup " shape groups of containers install in agalmatolite transmission medium;
4) by step 3) the agalmatolite assembly that obtains is placed in the CS-IIID artificial diamond hydraulic machine (the large press of cubic apparatus) that Guilin Metallurgy Machinery Principal Station manufactures and suppresses, the oil pressure of pressing process is that 40MPa (shows the pressure calibration of press cavity, the pressure at about 13MPa oil pressure respective chamber center is 1GPa), the pressure at respective chamber center is 3GPa, and the dwell time is 3min;
5) take out the complete block sample of compacting after release, obtain described Ag 2te block thermoelectric material.
Fig. 7 is the XRD figure spectrum of the present embodiment products therefrom, and showing products therefrom in figure is good Ag 2te is single-phase, and under room temperature is described, imposing 3GPa high pressure to Ag powder and Te powder can synthesize Ag in 3min 2te compound.Utilize Archimedes method to test product density, its density is 97.8%, and this high-pressure method technology of preparing is not only supper-fast as seen obtains target compound, and a step achieves densification simultaneously.Microscopic appearance sign is carried out to products therefrom section, the results are shown in Figure 8, show 10-50nm crystal grain in figure and be agglomerated into coarse particles under High Pressure, size is about 0.5-2 μm, the multiple dimensioned construction structure of such one, can effective scattering phonon, reduce the thermal conductivity of products therefrom, be conducive to the thermoelectricity capability improving product.To carry out electronic probe microcell back scattering observation after its surface polishing as shown in Figure 9, contrast is consistent, shows product chemistry distributed components, does not have obvious second-phase to produce, proved the validity of present method further.Figure 10 is that product thermal diffusivity and thermal conductivity vary with temperature curve, and its thermal conductivity rises with temperature and declines, and in whole warm area, (300-400K) all keeps lower level, is 0.5-0.8W.m -1k -1.Figure 11 is that products therefrom power factor and zero dimension thermoelectric figure of merit ZT vary with temperature curve, 127 DEG C time, and ZT max=0.7, higher than sample prepared by long-time adhere annealing technology.
For technical solutions according to the invention, stoichiometrically (1.8 ~ 2): take elemental powders Ag, X powder in (1 ~ 1.1) scope as reactant, wherein X is Se or Te, within the scope of this, take the circumstances into consideration the stoichiometric ratio of both adjustment, all can realize technical scheme of the present invention; In addition in pressing process, pressurize 1 ~ 5min under 2 ~ 5GPa, also all can realize technical scheme of the present invention, not enumerate embodiment at this.
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some improvement and conversion, these all belong to protection scope of the present invention.

Claims (7)

1. an Ag 2the supper-fast synthetic method of X block thermoelectric material, is characterized in that, mixing raw material, is suppressed after mixing for raw material with Ag and X simple substance by normal temperatures under pressure field effect, obtained fine and close Ag 2x block thermoelectric material, wherein X is Se or Te.
2. Ag according to claim 1 2the supper-fast synthetic method of X block thermoelectric material, is characterized in that, the mol ratio between described simple substance Ag and X is (1.8 ~ 2): (1 ~ 1.1).
3. Ag according to claim 1 2the supper-fast synthetic method of X block thermoelectric material, is characterized in that, described pressing process is: pressurize 1 ~ 5min under 2 ~ 5GPa.
4. Ag according to claim 1 2the supper-fast synthetic method of X block thermoelectric material, is characterized in that, described pressing process is: pressurize 1 ~ 5min under 2.5 ~ 3.5GPa.
5. Ag according to claim 1 2the supper-fast synthetic method of X block thermoelectric material, is characterized in that, can obtain fine and close Ag in 15min 2x block thermoelectric material.
6. the Ag that method described in any one of Claims 1 to 5 is obtained 2x block thermoelectric material, is characterized in that, under 107 DEG C of temperature condition, and Ag 2the thermoelectric figure of merit ZT of Se block thermoelectric material max=0.65; Under 127 DEG C of temperature condition, Ag 2the thermoelectric figure of merit ZT of Te block thermoelectric material max=0.7.
7. Ag according to claim 6 2x block thermoelectric material, is characterized in that, by described Ag 2se block thermoelectric material is heated to 250 ~ 350 DEG C of annealing 1.5 ~ 2.5h under vacuum-sealing condition, and must anneal Ag 2se block thermoelectric material, its thermoelectric figure of merit is ZT under 116 DEG C of temperature condition max=1.1.
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CN109728156A (en) * 2018-12-29 2019-05-07 昆明理工大学 A kind of Ag of Ag auto-dope2The preparation method of Te thermoelectric material
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CN113462943A (en) * 2021-06-11 2021-10-01 武汉理工大学 Ultra-fast preparation of high-performance YbAl3Method for bulk thermoelectric material
CN114408876A (en) * 2022-01-07 2022-04-29 武汉理工大学 High-strength high-plasticity silver telluride and preparation method thereof

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