CN104946917B - A kind of method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides - Google Patents
A kind of method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides Download PDFInfo
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Abstract
The method that the present invention relates to prepare silver telluride antimony thermoelectric material with binary tellurides for initiation material, specifically includes following steps: 1) weigh silver telluride and antimony telluride as initiation material according to certain mol proportion；2) by step 1) described initiation material mix homogeneously, it is pressed into block final vacuum and seals；3) by step 2) gained vacuum seal after block be warming up to reaction temperature 420～500 DEG C reaction 3～12h, obtain single-phase or near single-phase silver telluride antimony buttocks body；4) by step 3) gained ingot body grind after carry out discharge plasma sintering, obtain fine and close silver telluride antimony thermoelectric material.The method is raw materials used stable in the air; the most oxidizable; it is prone to extensive, low-cost production; raw material preserves and mixed process is without protective atmosphere; reaction temperature is low, and technique is the most controlled, preparation cost is low, reproducible; and prepared silver telluride antimony regulus body material density height, thermoelectricity capability is excellent.
Description
Technical field
The invention belongs to new energy materials field, be specifically related to one and prepare silver telluride antimony thermoelectricity with binary tellurides for initiation material
The method of material.
Background technology
Thermoelectric material is a kind of thermoelectric effect (Seebeck effect) utilizing semi-conducting material and Peltier effect (Peliter
Effect) realize the functional material of direct conversion between heat energy and electric energy.Thermoelectric generating device is a kind of complete static generation technology, nothing
Need the power transmission of cylinder, piston and the complexity of conventional heat engines indispensability.Thermoelectric generating device is generally of device structure letter
List, low noise, nothing abrasion, No leakage, long-term reliability advantages of higher.Thermoelectric power generation technology is in military, boat at present
My god, the field such as medical science, microelectronics there is important effect.Along with the Fossil fuels such as oil, coal and natural gas are exhausted by market
With the worry of geopolitics, thermoelectric generation is just attract increasing concern as a kind of emerging green energy resource technology.By
The thermo-electric device that p-type and n-type semi-conductor thermoelectric material collectively constitute is the core component of thermoelectric generating device, and its conversion efficiency is certainly
Determine the conversion efficiency of thermoelectric heat generation system.The conversion efficiency of thermo-electric device depends on the performance figure of merit ZT (material of thermoelectric material
The characterization parameter of Thermal Synthetic electrical property) and the system temperature difference.Conventional thermoelectric materials mainly includes 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 has nearly reached business pole
Limit.Present stage researcher is just making great efforts to expand to the application of thermoelectric power generation technology solar photoelectric-thermoelectricity compound power-generating, work
Industry low-density waste heat recovery and automobile (comprising water surface ship and the submarines such as mammoth tanker) motor exhaust reclaim.With regard to vehicle exhaust
For recycling with the low-density thermal source such as industrial exhaust heat, replace in the urgent need to opening up eco-friendly Novel middle-temperature thermoelectric material at present
For lead telluride material.
Silver telluride antimony (AgSbTe2) it is middle warm electricity one of the material system paid high attention in the world.Known the most ternary
In compound, silver telluride antimony has the highest thermoelectric figure of merit.Due to its special crystal structure, electronic band structure and phonon vibration
Spectrum, silver telluride antimony shows extremely low thermal conductivity and bigger Seebeck coefficient in room temperature to 450 DEG C interval.By regulation
The stoichiometric proportion of each component, AgSbTe2Compound heat, electronic transport performance can optimize in a big way.Merit attention
, this material all has good thermoelectricity transmission characteristic in room temperature to whole temperature range, this vehicle exhaust and industry just
Warm area corresponding to heat recovery.
The preparation of silver telluride antimony is typically with high purity elemental as initiation material.Due to the chemical property that simple substance raw material is active, its harshness
Preservation condition and complicated operating procedure unavoidably add complexity and the nonrepeatability of preparation process, constrain material
Large-scale production is developed.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides the one with binary tellurides to be
Initiation material prepares the method for silver telluride antimony thermoelectric material, and reaction raw materials is stable in the air, and preparation process technique is the most controlled,
And prepared silver telluride antimony regulus body material density height, reproducible, thermoelectricity capability is excellent.
The present invention solves that the technical scheme that problem set forth above is used is:
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides, comprises the steps:
1) dispensing: according to the counterfeit binary phase diagraml of silver telluride-antimony telluride, according to mol ratio (50-x): (50+x) weigh silver telluride and
Antimony telluride is as initiation material, and wherein x is 0～6 (wherein, during x=0, silver telluride and antimony telluride mol ratio are 1:1, corresponding
Silver telluride antimony (AgSbTe2) compound of exact chemical metering ratio)；
2) briquetting seals: by step 1) described initiation material mix homogeneously, it is pressed into block final vacuum and seals；
3) solid state reaction: by step 2) gained vacuum seal after block be warming up to reaction temperature 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 grind after carry out discharge plasma sintering, obtain fine and close telluride
Silver antimony (AgSbTe2) thermoelectric material.
By such scheme, step 1) described in binary tellurides silver telluride and antimony telluride be powder, particle diameter preferably 200 mesh with
Under.If use block material, then need to pulverize in advance, to ensure step 2) in initiation material be sufficiently mixed uniformly, Yi Jihou
Continuous step 3) in the adequacy of solid state reaction.
By such scheme, step 1) described in binary tellurides silver telluride and the purity of antimony telluride more than or equal to 99.5%.
By such scheme, step 2) described in the condition of mixing be: initiation material is sufficiently mixed grinding 30～60min.
By such scheme, step 2) described in the condition being pressed into block be: gained block density is theoretical not less than silver telluride antimony
The 70% of density.Wherein, the size of gained block is decided according to the actual requirements, and the size of compacting gained block is to end product
Purity is without impact.
By such scheme, step 3) in heating rate there is no specific requirement, heating rate faster or more slowly to preparing
Journey and end product impact thereof are little.This is the advantage brought due to initiation material of the present invention, initiation material binary tellurides tellurium
The problems such as change silver and antimony telluride are more stable in heating process, non-volatile, distillation, this also one of innovation having achieved the present invention,
Make silver telluride antimony (AgSbTe2) preparation condition of thermoelectric material requires to become to be more prone to realize, simultaneously preparation time on more
Control the most flexibly.The heating rate range of choice in the embodiment of the present invention is 0～50 DEG C/min.
By such scheme, if it is necessary, step 3) gained ingot body material pulverizes last, repeats step 2) and 3), so
After carry out step 4 again) purity of solid state reaction product can be improved.Certainly, for whether repeating step 2) and 3) to carry
The purity of high 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
Not less than 25MPa, sintering temperature is 400～500 DEG C, and sintering time is 1～30min.
The silver telluride antimony thermoelectric material that said method prepares, density is more than or equal to 6.94g/cm3(silver telluride antimony solid density
For 7.16g/cm3), relative density is more than 96%；Thermoelectricity capability index ZT maximum 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/cm3, thermoelectricity capability index ZT 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 diagraml of silver telluride-antimony telluride, and science determines both ratios and as initiation material, first
Obtain the single-phase of relatively low consistency or nearly single-phase silver telluride antimony slab body by solid state reaction, then use discharge plasma sintering skill
Art, obtains high density silver telluride antimony block thermoelectric material, and prepared silver telluride antimony regulus body material density is high, and purity is high, repeats
Property good, thermoelectricity capability is excellent, and performance is better than commercial lead telluride sample, and can prepare the sample of different sizes and shapes as required
Product.
2, compared with other preparation method, the present invention has abandoned traditional design with high purity elemental element as initiation material and has thought
Road, choosing binary tellurides highly stable under air atmosphere, that be readily available is raw material, effectively simplifies raw material and preserves and behaviour
Make condition, and due to the preferable stability of raw material, heating rate is not particularly limited by preparation process so that silver telluride antimony
(AgSbTe2) preparation condition of thermoelectric material requires to become to be more prone to realize, and is easier to control flexibly on preparation time simultaneously
System.
3, the present invention have employed solid state reaction combine with discharge plasma sintering technique and prepare silver telluride antimony (AgSbTe2) heat
Electric material, solid state reaction temperature is relatively low, consuming little energy in preparation process, it is easy to operation, discharge plasma sintering process
The most controlled so that whole preparation process time is short, reproducible, technique simply, the most controlled.
4, the binary tellurides used in the present invention all can, low cost extensive by wet chemistry method be prepared, reaction raw materials two
Unit's tellurides is stable in the air, the most oxidizable, it is easy to large-scale low-cost produces, and raw material preserves and mixed process is without protection
Atmosphere.
Accompanying drawing explanation
Fig. 1 is Powder x-ray diffraction (XRD) collection of illustrative plates (plasma discharging of products therefrom after solid state reaction in embodiment 1
Before sintering), in figure, vertical short-term is silver telluride antimony standard spectrum diffraction maximum position.
Fig. 2 is that Powder x-ray diffraction (XRD) collection of illustrative plates of the block silver telluride antimony thermoelectric material prepared by embodiment 1 (is put
After electricity plasma agglomeration), in figure, vertical short-term is silver telluride antimony standard spectrum diffraction maximum position.
Fig. 3 is the thermoelectricity capability figure of the silver telluride block antimony thermoelectric material prepared by embodiment 1.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office
It is limited to the following examples.
In following embodiment, binary tellurides silver telluride and antimony telluride are powder, and quality purity is more than or equal to 99.5%, particle diameter
Below preferably 200 mesh.
Embodiment 1
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides, comprises the steps:
1) dispensing: according to the counterfeit binary phase diagraml of silver telluride-antimony telluride, weigh silver telluride and antimony telluride as rising according to mol ratio 1:1
(being equivalent to (50-x): x=0 in (50+x) ratio, silver telluride is compared in the taken amount correspondence exact chemical metering of initiation material to beginning raw material
Antimonial), 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
Planting tellurides and be powder, particle diameter is below 200 mesh；
2) briquetting seals: by step 1) described initiation material puts into and is fully ground 60min under agate mortar, air atmosphere,
Then being pressed into the cylindric block of several a diameter of 12.7mm, the most about 3mm on tablet machine, gained block density is about
The 87% of silver telluride antimony density；Gained block is put into diameter 15mm, length about 12cm quartz ampoule, in vacuum 10-3Pa
Under the conditions of seal；
3) solid state reaction: by step 2) gained vacuum seal after quartz ampoule be placed in Muffle furnace, be warmed up to 5 DEG C/h of speed
300 DEG C, being then slowly warmed up to 460 DEG C with 1 DEG C/h of speed, insulation 6h (i.e. reacts 6h) under keeping warm mode, obtains the most single-phase
Silver telluride antimonial ingot body；
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig,
Carrying out discharge plasma sintering, sintering pressure is 50MPa, and sintering temperature is 480 DEG C, and sintering time is 5min, obtains high
Consistency silver telluride antimony block thermoelectric material, density is 7.10g/cm3。
Wherein, step 3) afterwards the XRD figure of products therefrom compose as it is shown in figure 1, sample principal phase is silver telluride antimonial, deposit
At the miscellaneous peak of a small amount of low-intensity, may be by the unreacted of trace silver telluride Ag completely2Te and antimony telluride Sb2Te3Cause.
Fig. 2 is step 4) the XRD figure spectrum of gained block after discharge plasma sintering, for single-phase silver telluride antimonial, miscellaneous
Peak is negligible substantially, and gained block after discharge plasma sintering is it is believed that be silver telluride antimony block thermoelectric material, initial former
Material is substantially completely converted into target product silver telluride antimonial.
The thermoelectricity capability of the high-compactness silver telluride antimony block thermoelectric material obtained by the present embodiment is shown in Fig. 3, carrys out table by ZT value
Levy, near 360 DEG C, can reach 1.28.It should be noted that the present embodiment prepares material near room temperature more than 0.5,
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
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides, comprises the steps:
1) dispensing: according to mol ratio 48:52 weigh silver telluride and antimony telluride as initiation material (be equivalent to (50-x):
(50+x) x=2 in ratio), wherein, the quality purity of silver telluride is better than 99.99%, and the quality purity of antimony telluride is better than
99.999%, two kinds of tellurides are powder, and particle diameter is below 200 mesh；
2) briquetting seals: by step 1) described raw material puts into and is fully ground 60min, then under agate mortar, air atmosphere
Being pressed into the cylindric block of several a diameter of 12.7mm, the most about 3mm on tablet machine, gained block density is about telluride
The 82% of silver antimony density；Gained block is put into diameter 15mm, length about 12cm quartz ampoule, in vacuum 10-3Pa condition
Lower seal；
3) solid state reaction: by step 2) gained vacuum seal after quartz ampoule be placed in Muffle furnace, with 50 DEG C/h of speed heat up
To 300 DEG C, then slowly it is warmed up to 460 DEG C with 10 DEG C/h of speed, reacts 6h, obtain nearly single-phase silver telluride antimonial ingot body；
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig,
Carrying out discharge plasma sintering, sintering temperature is 420 DEG C, pressure 50MPa, and the time is 15min, obtains high-compactness telluride
Silver bullion body antimony thermoelectric material, density is 6.96g/cm3。
The thermoelectricity capability ZT value of the high-compactness silver telluride block antimony thermoelectric material obtained by the present embodiment near 340 DEG C up to
To 1.05, the present embodiment prepares material near room temperature more than 0.45, and this makes sample show Gao Ping at whole test warm area
All ZT value and conversion efficiency of thermoelectric.
In addition, it is necessary to explanation: in embodiment 2, solid state reaction all have employed with embodiment 1 and heats up stage by stage, heating rate
Differ relatively big with embodiment 1, and in example 3 below, the temperature-rise period of solid state reaction heats up the most stage by stage, but a step liter
Temperature, to reaction temperature, differ relatively big with embodiment 1,2, but regardless of whether intensification, heating rate or fast or the most equal stage by stage
Purity and performance to target product do not have a significant effect, and thus illustrate due to the preferable stability of initiation material, this preparation process
In heating rate and temperature-rise period are not particularly limited.It is initiation material according to high purity elemental element, then lives due to high purity elemental
The chemical property sprinkled, solid phase temperature-rise period necessarily has a rigors to heating rate, and the dispensing of front and continued and briquetting seal process
There is also the requirement of many harshnesses, to avoid oxygen and the moisture oxidation to simple substance raw material in air, this adds preparation virtually
Process and the complexity of equipment and nonrepeatability, constrain the large-scale production exploitation of this thermoelectric material.
Embodiment 3
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides, comprises the steps:
1) dispensing: according to mol ratio 44:56 weigh silver telluride and antimony telluride as initiation material (be equivalent to (50-x):
(50+x) x=6 in ratio), wherein the quality purity of silver telluride is better than 99.99%, and the quality purity of antimony telluride is better than
99.999%, two kinds of tellurides are powder, and particle diameter is below 200 mesh；
2) briquetting seals: by step 1) described raw material puts into and is fully ground 30min, then under agate mortar, air atmosphere
Being pressed into the cylindric block of several a diameter of 12.7mm, the most about 3.5mm on tablet machine, gained block density is about tellurium
Change the 73% of silver antimony density；Gained block is put into diameter 15mm, length about 12cm quartz ampoule, in vacuum 10-3Pa bar
Part lower seal；
3) solid state reaction: by step 2) gained vacuum seal after quartz ampoule be placed in Muffle furnace, with 20 DEG C/h of speed heat up
To 480 DEG C, react 12h, obtain nearly single-phase silver telluride antimonial ingot body；
4) discharge plasma sintering: by step 3) after gained ingot body crushing grinding, load in diameter 15mm graphite jig,
Carrying out discharge plasma sintering, sintering temperature is 460 DEG C, pressure 50MPa, and the time is 10min, obtains high-compactness telluride
Silver bullion body antimony thermoelectric material, density is 7.00g/cm3。
The thermoelectricity capability ZT value of the high-compactness silver telluride block antimony thermoelectric material obtained by the present embodiment near 300 DEG C up to
To 0.85, the present embodiment prepares material near room temperature more than 0.4, and this makes sample show Gao Ping at whole test warm area
All ZT value and conversion efficiency of thermoelectric.
The above is only the preferred embodiment of the present invention, it is noted that for the person of ordinary skill of the art,
On the premise of conceiving without departing from the invention, it is also possible to making some modifications and variations, these broadly fall into the protection model of the present invention
Enclose.
Claims (6)
1. the method preparing silver telluride antimony thermoelectric material with binary tellurides for initiation material, it is characterised in that comprise the steps:
1) dispensing: according to mol ratio (50-x): (50+x) weighs silver telluride and antimony telluride as initiation material, and wherein x is 0～6；
2) briquetting seals: by initiation material mix homogeneously described in step 1), is pressed into block final vacuum and seals；
3) solid state reaction: by step 2) gained vacuum seal after block be warming up to reaction temperature 420～500 DEG C reaction 3～12h, obtain single-phase silver telluride antimony buttocks body or nearly single-phase silver telluride antimony buttocks body；
4) discharge plasma sintering: carry out discharge plasma sintering after being ground by step 3) gained ingot body, obtain fine and close silver telluride antimony thermoelectric material；
Step 2) in be pressed into the condition of block and be: gained block density is not less than the 70% of silver telluride antimony solid density.
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides the most according to claim 1, it is characterised in that silver telluride and antimony telluride described in step 1) are powder, below particle diameter preferably 200 mesh.
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides the most according to claim 1, it is characterised in that silver telluride and the purity of antimony telluride described in step 1) are more than or equal to 99.5%.
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides the most according to claim 1, it is characterised in that step 2) in mixing condition be: by initiation material mixed grinding 30～60min.
The method preparing silver telluride antimony thermoelectric material for initiation material with binary tellurides the most according to claim 1, the condition that it is characterized in that the discharge plasma sintering in step 4) is: 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.
6. the silver telluride antimony thermoelectric material that the described method of one of claim 1-5 prepares.
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170104 Termination date: 20200522 |