CN104946917A - Method for preparing silver antimony telluride thermoelectric material by taking binary tellurides as start raw materials - Google Patents
Method for preparing silver antimony telluride thermoelectric material by taking binary tellurides as start raw materials Download PDFInfo
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Abstract
The invention relates to a method for preparing a silver antimony telluride thermoelectric material by taking binary tellurides as start raw materials. The method comprises the following specific steps: 1) weighing silver telluride and antimony telluride at a certain molar ratio as start raw materials; 2) uniformly mixing the start raw materials in the step 1), pressing into a block and performing vacuum sealing; 3) heating the block obtained after the vacuum sealing in the step 2) to a reaction temperature of 420-500 DEG C, and reacting for 3-12h to obtain a single-phase or near single-phase silver antimony telluride ingot; and 4) grinding the ingot obtained in the step 3), and performing spark plasma sintering to obtain a dense silver antimony telluride thermoelectric material. The raw materials adopted in the method are stable in air and hardly oxidized, and large-scale and low-cost production is easy to realize; a protective atmosphere is not needed the storage and mixing processes of the raw materials, the reaction temperature is low, the process is simple and controllable, the preparation cost is low, and the repeatability is good; and the prepared silver antimony telluride block material has high density and excellent thermoelectric performance.
Description
Technical field
The invention belongs to new energy materials field, be specifically related to a kind of with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material.
Background technology
Thermoelectric material is a kind of functional materials utilizing the thermoelectric effect of semiconductor material (Seebeck effect) and Peltier effect (Peliter effect) to realize directly conversion between heat energy and electric energy.Thermoelectric generating device is a kind of complete static generation technology, without the need to the power transmission of the cylinder of conventional heat engines indispensability, piston and complexity.Thermoelectric generating device has that device structure is simple usually, lower noise, without wearing and tearing, No leakage, long-term reliability advantages of higher.Current thermoelectric power generation technology has important effect in fields such as military affairs, space flight, medical science, microelectronics.Along with market to exhaust fossil oils such as oil, coal and Sweet natural gases and the worry of geopolitics, thermoelectric generation is just attract increasing concern as one emerging green energy resource technology.The thermo-electric device be jointly made up of p-type and n-type semi-conductor thermoelectric material is the core component of thermoelectric generating device, and its efficiency of conversion determines the efficiency of conversion of thermoelectric heat generation system.The efficiency of conversion of thermo-electric device depends on performance figure of merit ZT (characterization parameter of material Thermal Synthetic electrical property) and the system temperature difference of thermoelectric material.Conventional thermoelectric materials mainly comprises room temperature suitable material Tellurobismuthite and middle temperature suitable material lead telluride.Due to the toxicity of lead element, the middle temperature application of current conventional thermoelectric materials almost reaches the business limit.Present stage investigator is just making great efforts the Application Areas of thermoelectric power generation technology to be expanded to solar photoelectric-thermoelectricity compound power-generating, industrial low density waste heat recovery and automobile (comprising water surface ship and the submarines such as mammoth tanker) motor exhaust and is reclaiming.With regard to the low density such as vehicle exhaust and industrial exhaust heat thermal source is recycled, substitute lead telluride material in the urgent need to opening up eco-friendly Novel middle-temperature thermoelectric material at present.
Silver telluride antimony (AgSbTe
2) show great attention in the world in one of warm electric material system.In known simple ternary compound, silver telluride antimony has the highest thermoelectric figure of merit.Due to its special crystalline structure, electronic band structure and phonon vibration spectrum, silver telluride antimony shows extremely low thermal conductivity and larger Seebeck coefficient in room temperature to 450 DEG C interval.By regulating the stoichiometric ratio of each component, AgSbTe
2compound heat, electronic transport performance can be optimized in a big way.It should be noted that this material all has good thermoelectricity transport property in room temperature to whole temperature range, this is vehicle exhaust and the warm area corresponding to industrial afterheat recovery utilization just.
The preparation of silver telluride antimony is generally starting raw material with high purity elemental.Due to the chemical property that simple substance raw material is active, the preservation condition of its harshness and complicated operation steps unavoidably add complicacy and the nonrepeatability of preparation process, constrain the scale operation exploitation of material.
Summary of the invention
Technical problem to be solved by this invention be the deficiency that exists for above-mentioned prior art and provide a kind of with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, reaction raw materials is stable in the air, preparation process technique is simply controlled, and prepared silver telluride antimony regulus body material density is high, reproducible, thermoelectricity capability is excellent.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
With binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, comprise the steps:
1) prepare burden: according to the counterfeit binary phase diagram of silver telluride-antimony telluride, according to mol ratio (50-x): (50+x) takes silver telluride and antimony telluride as starting raw material, wherein x is 0 ~ 6 (wherein, during x=0, silver telluride and antimony telluride mol ratio are 1:1, silver telluride antimony (AgSbTe2) compound of corresponding exact chemical metering ratio);
2) briquetting sealing: by step 1) described starting raw material mixes, and is pressed into the sealing of block final vacuum;
3) solid state reaction: by step 2) block after gained vacuum-sealing is warming up to temperature of reaction 420 ~ 500 DEG C reaction 3 ~ 12h, obtains single-phase silver telluride antimony buttocks body or nearly single-phase silver telluride antimony buttocks body;
4) discharge plasma sintering: by step 3) gained ingot body grinding after carry out discharge plasma sintering, obtain fine and close silver telluride antimony (AgSbTe
2) thermoelectric material.
By such scheme, step 1) described in binary telluride silver telluride and antimony telluride be Powdered, particle diameter is preferably below 200 orders.If use block material, then need to pulverize in advance, to ensure step 2) in fully the mixing of starting raw material, and follow-up step 3) in the adequacy of solid state reaction.
By such scheme, step 1) described in binary telluride silver telluride and the purity of antimony telluride be more than or equal to 99.5%.
By such scheme, step 2) described in the condition of mixing be: by abundant for starting raw material mixed grinding 30 ~ 60min.
By such scheme, step 2) described in the condition being pressed into block be: gained block density is not less than 70% of silver telluride antimony theoretical density.Wherein, the size of gained block is decided according to the actual requirements, the size that obsession obtains block on the purity of final product without impact.
By such scheme, step 3) in temperature rise rate there is no specific requirement, temperature rise rate faster or more slowly on preparation process and final product impact little.This is the advantage because starting raw material of the present invention brings, and the problems such as starting raw material binary telluride silver telluride and antimony telluride is more stable in heat-processed, non-volatile, distillation, this has also achieved one of innovation of the present invention, makes silver telluride antimony (AgSbTe
2) preparation condition of thermoelectric material requires to become and be more prone to realize, preparation time more easily controls flexibly simultaneously.Temperature rise rate range of choice in the embodiment of the present invention is 0 ~ 50 DEG C/min.
By such scheme, if necessary, step 3) after gained ingot body ground material powdered, repeating step 2) and 3), and then carry out step 4) purity of solid state reaction product can be improved.Certainly, the repeating step 2 for whether) and 3) to improve the purity of solid state reaction product, can select with practical situation according to the actual requirements.
By such scheme, step 4) described in the condition of discharge plasma sintering be: under vacuum or inert atmosphere, sintering pressure is not less than 25MPa, and sintering temperature is 400 ~ 500 DEG C, and sintering time is 1 ~ 30min.
The silver telluride antimony thermoelectric material that aforesaid method prepares, density is more than or equal to 6.94g/cm
3(silver telluride antimony theoretical density is 7.16g/cm
3), relative density is greater than 96%; Thermoelectricity capability index ZT maximum value is not less than 0.85, and room temperature is not less than 0.4; When wherein x is 0, gained silver telluride antimony thermoelectric material density is 7.10g/cm
3, thermoelectricity capability index ZT is maximum reaches 1.28.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention is according to the counterfeit binary phase diagram of silver telluride-antimony telluride, science determine both ratio and as starting raw material, first the single-phase of relatively low density or nearly single-phase silver telluride antimony slab body is obtained by solid state reaction, then discharge plasma sintering technique is adopted, obtain high-density silver telluride antimony block thermoelectric material, prepared silver telluride antimony regulus body material density is high, purity is high, reproducible, thermoelectricity capability is excellent, performance is better than commercial lead telluride sample, and can prepare the sample of different size and shape as required.
2, compared with other preparation method, the present invention has abandoned traditional mentality of designing being starting raw material with high purity elemental element, the binary telluride of highly stable under choosing air atmosphere, easy acquisition is raw material, effectively simplify raw material to preserve and operational condition, and due to the good stability of raw material, in preparation process, temperature rise rate is not particularly limited, makes silver telluride antimony (AgSbTe
2) preparation condition of thermoelectric material requires to become and be more prone to realize, preparation time more easily controls flexibly simultaneously.
3, have employed solid state reaction in the present invention to combine with discharge plasma sintering technique and prepare silver telluride antimony (AgSbTe
2) thermoelectric material, solid state reaction temperature is relatively low, consuming little energy in preparation process, easy handling, and discharge plasma sintering process is simply controlled, such that whole preparation process time is short, reproducible, technique simply, controlled flexibly.
4, the binary telluride used in the present invention is all extensive by wet chemistry method, low cost preparation, and reaction raw materials binary telluride is stable in the air, not oxidizable, is easy to large-scale low-cost and produces, and raw material preservation and mixing process are without the need to protective atmosphere.
Accompanying drawing explanation
Fig. 1 is Powder x-ray diffraction (XRD) collection of illustrative plates (before discharge plasma sintering) of products therefrom after solid state reaction in embodiment 1, and in figure, vertical short-term is silver telluride antimony standard spectrum diffraction peak position.
Fig. 2 is Powder x-ray diffraction (XRD) collection of illustrative plates (after discharge plasma sintering) of the block silver telluride antimony thermoelectric material prepared by embodiment 1, and in figure, vertical short-term is silver telluride antimony standard spectrum diffraction peak position.
Fig. 3 is the thermoelectricity capability figure of the silver telluride block antimony thermoelectric material prepared by embodiment 1.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but the present invention is not only confined to the following examples.
In following embodiment, binary telluride silver telluride and antimony telluride are Powdered, and quality purity is more than or equal to 99.5%, and particle diameter is preferably below 200 orders.
Embodiment 1
With binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, comprise the steps:
1) prepare burden: according to the counterfeit binary phase diagram of silver telluride-antimony telluride, silver telluride is taken and antimony telluride (is equivalent to (50-x): x=0 in (50+x) ratio as starting raw material according to mol ratio 1:1, the corresponding exact chemical metering of taken amount of starting raw material is than silver telluride antimony compounds), wherein, the quality purity of silver telluride is better than in 99.99%; The quality purity of antimony telluride is better than 99.999%; Two kinds of tellurides are Powdered, and particle diameter is below 200 orders;
2) briquetting sealing: by step 1) described starting raw material puts into agate mortar, fully 60min is ground under air atmosphere, then on tabletting machine, be pressed into the cylindric block that several diameter is 12.7mm, highly about 3mm, gained block density is about 87% of silver telluride antimony density; Gained block is put into diameter 15mm, length is about 12cm silica tube, in vacuum 10
-3pa condition lower seal;
3) solid state reaction: by step 2) silica tube after gained vacuum-sealing is placed in retort furnace, 300 DEG C are warmed up to speed 5 DEG C/h, then 460 DEG C are slowly warmed up to speed 1 DEG C/h, insulation 6h (namely reacting 6h under keeping warm mode), obtains nearly single-phase silver telluride antimony compounds ingot body;
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig, carry out discharge plasma sintering, sintering pressure is 50MPa, sintering temperature is 480 DEG C, sintering time is 5min, and obtain high-compactness silver telluride antimony block thermoelectric material, density is 7.10g/cm
3.
Wherein, step 3) afterwards products therefrom XRD figure spectrum as shown in Figure 1, sample principal phase is silver telluride antimony compounds, there is a small amount of low strength and to mix peak, may by the unreacted of trace silver telluride Ag completely
2te and antimony telluride Sb
2te
3cause.
Fig. 2 is step 4) the XRD figure spectrum of gained block after discharge plasma sintering, for single-phase silver telluride antimony compounds, assorted peak is substantially negligible, after discharge plasma sintering, gained block can think that starting raw material is converted into target product silver telluride antimony compounds substantially completely for silver telluride antimony block thermoelectric material.
The thermoelectricity capability of the high-compactness silver telluride antimony block thermoelectric material that the present embodiment obtains is shown in Fig. 3, characterizes, can reach 1.28 by ZT value near 360 DEG C.It should be noted that the present embodiment is prepared material and is greater than 0.5 near room temperature, this makes sample show high average ZT value and conversion efficiency of thermoelectric at whole test warm area (about 20 ~ 400 DEG C).
Embodiment 2
With binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, comprise the steps:
1) prepare burden: take silver telluride and antimony telluride as starting raw material (being equivalent to (50-x): x=2 in (50+x) ratio) according to mol ratio 48:52, wherein, the quality purity of silver telluride is better than 99.99%, the quality purity of antimony telluride is better than 99.999%, two kinds of tellurides are Powdered, and particle diameter is below 200 orders;
2) briquetting sealing: by step 1) described raw material puts into agate mortar, fully 60min is ground under air atmosphere, then on tabletting machine, be pressed into the cylindric block that several diameter is 12.7mm, highly about 3mm, gained block density is about 82% of silver telluride antimony density; Gained block is put into diameter 15mm, length is about 12cm silica tube, in vacuum 10
-3pa condition lower seal;
3) solid state reaction: by step 2) silica tube after gained vacuum-sealing is placed in retort furnace, and be warmed up to 300 DEG C with speed 50 DEG C/h, be then slowly warmed up to 460 DEG C with speed 10 DEG C/h, reaction 6h, obtains nearly single-phase silver telluride antimony compounds ingot body;
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig, carry out discharge plasma sintering, sintering temperature is 420 DEG C, pressure 50MPa, time is 15min, and obtain high-compactness silver telluride block antimony thermoelectric material, density is 6.96g/cm
3.
The thermoelectricity capability ZT value of the high-compactness silver telluride block antimony thermoelectric material that the present embodiment obtains can reach 1.05 near 340 DEG C, the present embodiment is prepared material and is greater than 0.45 near room temperature, and this makes sample show high average ZT value and conversion efficiency of thermoelectric at whole test warm area.
In addition, it should be noted that: in embodiment 2, solid state reaction and embodiment 1 all have employed and heat up stage by stage, temperature rise rate differs larger with embodiment 1, and below in embodiment 3 temperature-rise period of solid state reaction do not heat up stage by stage, but a step is warming up to temperature of reaction, differ larger with embodiment 1,2, but no matter whether heat up stage by stage, temperature rise rate is fast or all do not have a significant effect to the purity of target product and performance slowly, illustrate thus due to the good stability of starting raw material, in this preparation process, temperature rise rate and temperature-rise period are not particularly limited.Be starting raw material according to high purity elemental element, then due to chemical property that high purity elemental is active, solid phase temperature-rise period must have rigors to temperature rise rate, and also there is the requirement of many harshnesses in the batching of front and continued and briquetting seal process, to avoid in air oxygen and moisture to the oxidation of simple substance raw material, this adds complicacy and the nonrepeatability of preparation process and equipment virtually, constrains the scale operation exploitation of this thermoelectric material.
Embodiment 3
With binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, comprise the steps:
1) prepare burden: take silver telluride and antimony telluride as starting raw material (being equivalent to (50-x): x=6 in (50+x) ratio) according to mol ratio 44:56, wherein the quality purity of silver telluride is better than 99.99%, the quality purity of antimony telluride is better than 99.999%, two kinds of tellurides are Powdered, and particle diameter is below 200 orders;
2) briquetting sealing: by step 1) described raw material puts into agate mortar, fully 30min is ground under air atmosphere, then on tabletting machine, be pressed into the cylindric block that several diameter is 12.7mm, highly about 3.5mm, gained block density is about 73% of silver telluride antimony density; Gained block is put into diameter 15mm, length is about 12cm silica tube, in vacuum 10
-3pa condition lower seal;
3) solid state reaction: by step 2) silica tube after gained vacuum-sealing is placed in retort furnace, and be warmed up to 480 DEG C with speed 20 DEG C/h, reaction 12h, obtains nearly single-phase silver telluride antimony compounds ingot body;
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig, carry out discharge plasma sintering, sintering temperature is 460 DEG C, pressure 50MPa, time is 10min, and obtain high-compactness silver telluride block antimony thermoelectric material, density is 7.00g/cm
3.
The thermoelectricity capability ZT value of the high-compactness silver telluride block antimony thermoelectric material that the present embodiment obtains can reach 0.85 near 300 DEG C, the present embodiment is prepared material and is greater than 0.4 near room temperature, and this makes sample show high average ZT value and conversion efficiency of thermoelectric at whole test warm area.
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. with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that comprising the steps:
1) prepare burden: according to mol ratio (50-x): (50+x) takes silver telluride and antimony telluride as starting raw material, and wherein x is 0 ~ 6;
2) briquetting sealing: by step 1) described starting raw material mixes, and is pressed into the sealing of block final vacuum;
3) solid state reaction: by step 2) block after gained vacuum-sealing is warming up to temperature of reaction 420 ~ 500 DEG C reaction 3 ~ 12h, obtains single-phase silver telluride antimony buttocks body or nearly single-phase silver telluride antimony buttocks body;
4) discharge plasma sintering: by step 3) gained ingot body grinding after carry out discharge plasma sintering, obtain fine and close silver telluride antimony thermoelectric material.
2. according to claim 1 with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that step 1) described in silver telluride and antimony telluride be Powdered, particle diameter is preferably below 200 orders.
3. according to claim 1 with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that step 1) described in silver telluride and the purity of antimony telluride be more than or equal to 99.5%.
4. according to claim 1 with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that step 2) in the condition of mixing be: by starting raw material mixed grinding 30 ~ 60min.
5. according to claim 1 with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that step 2) in be pressed into block condition be: gained block density is not less than 70% of silver telluride antimony theoretical density.
6. according to claim 1 with binary telluride for starting raw material prepares the method for silver telluride antimony thermoelectric material, it is characterized in that step 4) in the condition of discharge plasma sintering be: under vacuum or inert atmosphere, sintering pressure is not less than 25MPa, sintering temperature is 400 ~ 500 DEG C, and sintering time is 1 ~ 30min.
7. the silver telluride antimony thermoelectric material for preparing of the described method of one of claim 1-6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101532097A (en) * | 2009-04-13 | 2009-09-16 | 浙江大学 | Method for preparing silver antimony tellurium and silver telluride based on-site composite thermoelectric material |
| US20090250651A1 (en) * | 2008-04-04 | 2009-10-08 | Samsung Electronics Co., Ltd. | Dichalcogenide thermoelectric material |
| CN101956110A (en) * | 2010-10-19 | 2011-01-26 | 武汉理工大学 | Method for preparing Mg2BIV-based thermoelectric material by low-temperature solid-phase reaction |
| CN102674270A (en) * | 2012-05-25 | 2012-09-19 | 武汉理工大学 | Method for preparing Cu2Se thermoelectric material by low-temperature solid-phase reaction |
| KR101395565B1 (en) * | 2012-09-17 | 2014-05-15 | 한국세라믹기술원 | Manufacturing method of bismuth telluride thermoelectric material |
-
2015
- 2015-05-22 CN CN201510265983.6A patent/CN104946917B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090250651A1 (en) * | 2008-04-04 | 2009-10-08 | Samsung Electronics Co., Ltd. | Dichalcogenide thermoelectric material |
| CN101532097A (en) * | 2009-04-13 | 2009-09-16 | 浙江大学 | Method for preparing silver antimony tellurium and silver telluride based on-site composite thermoelectric material |
| CN101956110A (en) * | 2010-10-19 | 2011-01-26 | 武汉理工大学 | Method for preparing Mg2BIV-based thermoelectric material by low-temperature solid-phase reaction |
| CN102674270A (en) * | 2012-05-25 | 2012-09-19 | 武汉理工大学 | Method for preparing Cu2Se thermoelectric material by low-temperature solid-phase reaction |
| KR101395565B1 (en) * | 2012-09-17 | 2014-05-15 | 한국세라믹기술원 | Manufacturing method of bismuth telluride thermoelectric material |
Non-Patent Citations (6)
| Title |
|---|
| JOVOVIC V等: "Measurements of the energy band gap and valence band structure of AgSbTe2", 《PHYSICAL REVIEW B》 * |
| S.N.ZHANG: "Improvements of Thermoelectric Performances in AgSbTe2 System with in-situ Ag2Te Nano-precipitations", 《MATERIALS RESEARCH SOCIETY》 * |
| 徐静静等: "AgSbTe2热电化合物的超声化学合成法", 《无机材料学报》 * |
| 李涵等: "《熔体旋甩法制备高性能纳米结构方钴矿热电材料》", 30 June 2012, 武汉理工大学出版社 * |
| 杜保立等: "非化学计量比AgSbTe2+x化合物制备及热电性能", 《物理学报》 * |
| 樊浩天等: "高压制备AgSbTe2的微结构及高温电学性能研究", 《功能材料》 * |
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