CN104022218A - High-performance SbAgSeS-based thermoelectric material and preparation method thereof - Google Patents
High-performance SbAgSeS-based thermoelectric material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance SbAgSeS-based thermoelectric material. The chemical formula of the high-performance SbAgSeS-based thermoelectric material is SbAgSeS1-xClx, wherein x ranges from 0 to 0.05. The new-generation high-performance SbAgSeS-based thermoelectric material is developed for the first time, a highly pure single-phase SbAgSeS compound can be obtained through simple melting reaction, and the compact SbAgSeS-based blocky thermoelectric material can be prepared by combining a plasma sintering method. More importantly, the technology of combining combustion synthesis and plasma activated sintering is introduced for the first time, the compact SbAgSeS-based blocky thermoelectric material can be prepared in 20 min, the preparation process is ultra fast, the requirement for equipment is low, the preparation method is suitable for large-scale production, the technology is simple, and energy conversation and environment protection are achieved.
Description
Technical field
The invention belongs to new energy materials preparing technical field, be specifically related to a kind of high-performance SbAgSeS base thermoelectricity material and preparation method thereof.
Background technology
In recent ten years, population rapid expansion, industrial fast development, the energy and environmental problem highlight gradually, and energy crisis and environmental crisis cause concern day by day.At present, in the annual energy consuming in the whole world, approximately there is 70% form with used heat to be wasted, if these used heat effectively can be recycled, will alleviate greatly energy starved problem.Thermoelectric material can directly become electric energy by thermal power transfer, has the advantages such as, noiselessness little without drive disk assembly, volume, pollution-free, good reliability, recycles, having huge application prospect aspect industrial afterheat power generation in automobile waste heat.The conversion efficiency of thermoelectric material is by dimensionless thermoelectric figure of merit ZT (ZT=α
2σ T/ κ wherein α is that Seebeck coefficient, σ are that conductivity, k are that thermal conductivity, T are absolute temperature) determine.ZT is larger, and the conversion efficiency of thermoelectric of material is higher.
The at present research of thermoelectric material mainly concentrates on high power factor system, mainly adopts ball milling, melt to revolve to get rid of, the technology such as solid solution alloying, structure nano strengthens the scattering to phonon, reduces lattice thermal conductivity, thereby reaches the object of optimizing thermoelectricity capability.It is exactly its minimum lattice thermal conductivity that but the reduction of thermal conductivity has its limit, noncrystalline state eventually.Therefore, choose the compound of intrinsic lower thermal conductivity, by optimizing its power factor, improve thermoelectricity capability and seem very important.After all, the optimization of power factor is hard-core in theory.
BiAgSeS compounds is the compound that a class has intrinsic lower thermal conductivity, there is excellent thermoelectricity capability, and equally not containing rare element T e, but Bi is strategic element, reserves are not very high, therefore study the relatively abundant compounds of the same clan of raw material and necessitate.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of high-performance SbAgSeS base thermoelectricity material for the deficiency of above-mentioned prior art existence, and has explored the multiple preparation method of this thermoelectric material, and has studied its thermoelectricity capability.
A high-performance SbAgSeS base thermoelectricity material, its chemical formula is SbAgSeS
1-xcl
x, wherein x is 0-0.05.
The preparation method of above-mentioned high-performance SbAgSeS base block thermoelectric material is: first adopt fusion method or combustion synthesis method to prepare SbAgSeS original washing powder body heat electric material, then adopt plasma agglomeration method to prepare fine and close high-performance SbAgSeS base block thermoelectric material.
Press such scheme, it is as follows that described fusion method prepares the concrete grammar of SbAgSeS original washing powder body heat electric material: according to chemical formula SbAgSeS
1-xcl
x(x=0-0.05) in, the stoichiometric proportion of each element weighs after simple substance Sb, simple substance Ag, simple substance Se, simple substance S and silver chlorate AgCl mix and obtains reactant, by the cooling ingot body that obtains after described reactant vacuum seal melting, described ingot body is pulverized, and is SbAgSeS original washing powder body heat electric material.
Press such scheme, in described fusion method, the purity of simple substance Sb, simple substance Ag, simple substance Se, simple substance S is more high better, and purity more than 99% can prepare SbAgSeS base block thermoelectric material conventionally.
Press such scheme, in described fusion method the temperature of melting 750 ℃ or more than, preferred 750-900 ℃, the preferred time of melting is 1-6h, makes it abundant reaction.
Press such scheme, the intensification mechanism in described fusion method is preferably: first the speed with 1-3 ℃/min is raised to 400-500 ℃, then is raised to melt temperature with the speed of 3-7 ℃/min.
Press such scheme, described in be cooled to the cooling or quench cooled of nature, the quenching medium that described quench cooled adopts can be saturated aqueous common salt or liquid nitrogen etc.
Press such scheme, it is as follows that described combustion synthesis method prepares the concrete grammar of SbAgSeS original washing powder body heat electric material: according to chemical formula SbAgSeS
1-xcl
x(x=0-0.05) in, the stoichiometric proportion of each element weighs after simple substance Sb, simple substance Ag, simple substance Se, simple substance S and silver chlorate AgCl mix and obtains reactant, and caused combustion synthesis reaction, the cooling ingot body that obtains afterwards, described ingot body is pulverized, and is SbAgSeS original washing powder body heat electric material.
Press such scheme, in described combustion synthesis method, simple substance Sb, simple substance Ag, simple substance Se, simple substance S are powder, and purity more than 99% can prepare SbAgSeS base block thermoelectric material conventionally.
Press such scheme, the reactant of described combustion synthesis method is powder or is pressed into block.
Press such scheme, the atmosphere of described combustion synthesis method is vacuum or inert gas.
Press such scheme, any one in the self propagating high temperature synthesis model of employing one end igniting of described combustion synthesis method or the thermal explosion synthesis model that integral body is ignited.
Press such scheme, the temperature that the thermal explosion synthesis model that described integral body is ignited adopts is more than 400 ℃, preferred 400-600 ℃, and the time is no more than 2min.
Press such scheme, the condition of described plasma activated sintering is: sintering temperature is 400-500 ℃, and sintering pressure is 20-40MPa, and temperature retention time is 5-7min.
Press such scheme, the intensification mechanism in described plasma activated sintering is preferably: first the speed with 70-100 ℃/min is raised to 150-200 ℃, then is raised to sintering temperature with the speed of 20-50 ℃/min.
SbAgSeS base block thermoelectric material prepared by the present invention, when undoping Cl, described SbAgSeS base block thermoelectric material is the good Emission in Cubic SbAgSeS compound of crystalline phase, and ZT obtains maximum 0.12 in the time of 400 ℃.And the present invention can adulterate to SbAgSeS base thermoelectricity material effectively, such as at Se/S position doping halogen, Ag position doped with II A JiIIB family element, the Sb Bi of the same clan etc. that adulterates position.
Take foregoing as basis, do not departing under the prerequisite of basic fundamental thought of the present invention, according to ordinary skill knowledge and the means of this area, to its content, can also have modification, replacement or the change of various ways.
SbAgSeS compound and BiAgSeS compound Shu Tong gang, its compd B iAgSeS of the same clan has excellent thermoelectricity capability, and equally not containing rare element T e.SbAgSeS compound is the compound that a class has intrinsic lower thermal conductivity, yet there are no its relevant report, blank out especially aspect thermoelectricity capability, and it is very urgent that the research that it is carried out to thermoelectricity capability seems, has important scientific meaning.
The present invention has developed high-performance SbAgSeS base thermoelectricity material of new generation first, by simple frit reaction, can obtain extremely pure single-phase SbAgSeS compound, in conjunction with plasma agglomeration legal system for fine and close SbAgSeS base block thermoelectric material.What is more important, the present invention introduces combustion synthesis method, utilizes reaction self heat release, can prepare single-phase SbAgSeS original washing powder body heat electric material, and prepare SbAgSeS base block thermoelectric material in conjunction with plasma agglomeration within the extremely short time.The present invention introduces first burning and synthesizes in conjunction with plasma activated sintering technology, can prepare fine and close SbAgSeS base block thermoelectric material in 20min, and preparation process is supper-fast, low for equipment requirements, suitability for scale production, and technique is simple, energy-conserving and environment-protective.In addition, raw material of the present invention source is abundant, has adopted Se powder and S powder, significant without Te base thermoelectricity material to development.
Accompanying drawing explanation
Fig. 1 is embodiment 1 step 1) and 2) the XRD collection of illustrative plates of product.
Fig. 2 is embodiment 1 step 2) thermal diffusion coefficient and the thermal conductivity of product vary with temperature relation curve.
Fig. 3 is embodiment 1 step 2) power factor and the dimensionless thermoelectric figure of merit of product vary with temperature relation curve.
Fig. 4 is embodiment 2 steps 1) and 2) the XRD collection of illustrative plates of product.
Fig. 5 is embodiment 3 steps 2) the XRD collection of illustrative plates of product.
Fig. 6 is embodiment 4 steps 2) the XRD collection of illustrative plates of product.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment, further illustrate content of the present invention, but content of the present invention is not only confined to the following examples.
Embodiment 1
The preparation method of high-performance SbAgSeS base block thermoelectric material, comprises the following steps:
1) fusion method: take Sb piece, Ag silk, Se piece, S powder as raw material by stoichiometric proportion 1:1:1:1, raw material total amount is 5g, obtains reactant after mixing; Reactant is put into the sealing of quartz glass tube final vacuum, make reactant in vacuum atmosphere, put into vertical melting furnace, speed with 2 ℃/min is raised to 450 ℃, speed with 5 ℃/min is raised to 750 ℃ again, after insulation 5h, with the cooling ingot body that obtains of stove, described ingot body is put into agate mortar levigate, be SbAgSeS original washing powder body heat electric material;
2) taking 4g step 1) gained powder packs compacting in the graphite jig of Φ 15mm into, then graphite jig is put into plasma activated sintering (PAS) equipment, under vacuum condition below 10Pa and 30MPa pressure, with 90 ℃/min, be raised to 180 ℃, with 35 ℃/min, be raised to 450 ℃ again, insulation 5min, cools to room temperature with the furnace after sintering finishes, and obtains fine and close high-performance SbAgSeS base block thermoelectric material.
The quality purity of the present embodiment Raw Sb piece, Se piece, S powder is that the quality purity of 99.999%, Ag silk is 99.99%.
The present embodiment products therefrom is carried out to phase composition analysis and thermoelectricity capability test, Fig. 1 is the present embodiment step 1) and the XRD collection of illustrative plates of (2) product, as seen from the figure, after melting, after gained ingot body and plasma agglomeration, gained block is good Emission in Cubic SbAgSeS compound.
Fig. 2 is step 2) thermal diffusion coefficient and the thermal conductivity of product vary with temperature relation curve.As shown in Figure 2, within the scope of whole warm area, thermal diffusion coefficient and thermal conductivity all remain on extremely low-level, and do not vary with temperature, this determines by its intrinsic properties, and Sb skin has lone pair electrons, has neither part nor lot in into key, other covalent bonds are produced to repulsive interaction, the anharmonicity of whole lattice vibration is strengthened, strong scattering phonon, lattice thermal conductivity is extremely low.
Fig. 3 is step 2) power factor and the dimensionless thermoelectric figure of merit of product vary with temperature relation curve.From 3 figure, power factor and ZT value all rise and increase with temperature, and in the time of 400 ℃, ZT obtains maximum 0.12.
Embodiment 2
The preparation method of high-performance SbAgSeS base block thermoelectric material, comprises the following steps:
1) fusion method: take Sb piece, Ag silk, Se piece, S powder as raw material by stoichiometric proportion 1:1:1:1, raw material total amount is 5g, obtains reactant after mixing; Reactant is put into the sealing of quartz glass tube final vacuum, make reactant in vacuum atmosphere, put into vertical melting furnace, speed with 2 ℃/min is raised to 450 ℃, speed with 5 ℃/min is raised to 750 ℃ again, after insulation 5h, put it at once normal temperature saturated common salt quenching-in water and obtain ingot body, described ingot body is put into agate mortar levigate, be SbAgSeS original washing powder body heat electric material;
2) taking 4g step 1) gained powder packs compacting in the graphite jig of Φ 15mm into, then graphite jig is put into plasma activated sintering (PAS) equipment, under vacuum condition below 10Pa and 30MPa pressure, with 90 ℃/min, be raised to 180 ℃, with 35 ℃/min, be raised to 450 ℃ again, insulation 5min, cools to room temperature with the furnace after sintering finishes, and obtains fine and close high-performance SbAgSeS base block thermoelectric material.
The quality purity of the present embodiment Raw Sb piece, Se piece, S powder is that the quality purity of 99.999%, Ag silk is 99.99%.
The present embodiment products therefrom is carried out to phase composition analysis, and Fig. 4 is the present embodiment step 1) and 2) the XRD collection of illustrative plates of product, as seen from the figure, melting quench gained ingot body and plasma agglomeration gained block are good Emission in Cubic SbAgSeS compound.
Embodiment 3
Combustion synthesis method: the method for the synthetic SbAgSeS base thermoelectricity material powder of different temperatures thermal explosion, it comprises the following steps:
1) by stoichiometric proportion 1:1:1:1, take Sb powder, Ag powder, Se powder and S powder as raw material, raw material total amount is 5g, in agate mortar, mixes, and the mixed powder obtaining is as reactant; Reactant is put into steel grinding tool, on tablet press machine, adopt the pressure of 6MPa pressurize 5min to make into Φ 12mm ingot body;
2) different temperatures thermal explosion is synthetic: ingot body is vacuum-sealed in quartz glass tube, then quartz glass tube is put into respectively rapidly to the constant temperature oven of 400 ℃, 450 ℃, after 2min, take out, naturally cooling afterwards, products therefrom is SbAgSeS original washing powder body heat electric material.
The quality purity of the present embodiment Raw Sb powder, Se powder and S powder is that the quality purity of 99.999%, Ag powder is 99.99%.
Above-mentioned product is carried out to phase composition analysis, Fig. 5 is the XRD collection of illustrative plates of the present embodiment product, as seen from the figure, 400 ℃ of above thermal explosion 2min, can obtain very pure Emission in Cubic SbAgSeS compound, be SbAgSeS original washing powder body heat electric material, can prepare corresponding block thermoelectric material by follow-up plasma agglomeration.
Embodiment 4
Combustion synthesis method: the method for the SbAgSeS base thermoelectricity material powder of the synthetic Cl doping of thermal explosion, it comprises the following steps:
1) by stoichiometric proportion 1:(1-x): 1:(1-x): x takes Sb powder, Ag powder, Se powder, S powder and AgCl powder as raw material, wherein x respectively value be 1%, 2%, 3%, 4%, 5%, raw material total amount is 5g, in agate mortar, mix, the mixed powder obtaining is as reactant; Reactant is put into steel grinding tool, on tablet press machine, adopt the pressure of 6MPa pressurize 5min to make into Φ 12mm ingot body;
2) thermal explosion is synthetic: described ingot body is vacuum-sealed in quartz glass tube, then quartz glass tube is put into rapidly to the constant temperature oven of the 450 ℃ initiation combustion reaction of detonating, after 2min, take out, naturally coolingly obtain single-phase SbAgSeS
1-xcl
xcompound.
Above-mentioned product is carried out to phase composition analysis.Fig. 6 is that x is when value is 1%, 2%, 3%, 4%, 5% respectively, the XRD collection of illustrative plates of the present embodiment product, as seen from the figure, 450 ℃ of thermal explosion 2min, all can obtain very pure Emission in Cubic SbAgSeS compound, realization is at the Effective Doping of S position, be the S position in SbAgSeS original washing powder body heat electric material Effective Doping Cl.The SbAgSeS base thermoelectricity material powder of this Effective Doping Cl can be prepared block thermoelectric material by follow-up plasma agglomeration.
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, without departing from the concept of the premise of the invention, can also make some improvement and conversion, and these all belong to protection scope of the present invention.
Claims (10)
1. a high-performance SbAgSeS base thermoelectricity material, the chemical formula that it is characterized in that it is SbAgSeS
1-xcl
x, wherein x is 0-0.05.
2. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 1, it is characterized in that it first adopts fusion method or combustion synthesis method to prepare SbAgSeS original washing powder body heat electric material, then adopts plasma agglomeration method to prepare fine and close high-performance SbAgSeS base block thermoelectric material.
3. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 2, is characterized in that described fusion method prepares the concrete grammar of SbAgSeS original washing powder body heat electric material as follows: according to chemical formula SbAgSeS
1- xcl
x(x=0-0.05) in, the stoichiometric proportion of each element weighs after simple substance Sb, simple substance Ag, simple substance Se, simple substance S and silver chlorate AgCl mix and obtains reactant, by the cooling ingot body that obtains after described reactant vacuum seal melting, described ingot body is pulverized, and is SbAgSeS original washing powder body heat electric material.
4. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 3, it is characterized in that melting in described fusion method 750 ℃ of temperature or more than, the melting time is 1-6h.
5. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 3, is cooled to the cooling or quench cooled of nature described in it is characterized in that, the quenching medium that described quench cooled adopts is saturated aqueous common salt or liquid nitrogen.
6. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 2, is characterized in that described combustion synthesis method prepares the concrete grammar of SbAgSeS original washing powder body heat electric material as follows: according to chemical formula SbAgSeS
1-xcl
x(x=0-0.05) in, the stoichiometric proportion of each element weighs after simple substance Sb, simple substance Ag, simple substance Se, simple substance S and silver chlorate AgCl mix and obtains reactant, and caused combustion synthesis reaction, the cooling ingot body that obtains afterwards, described ingot body is pulverized, and is SbAgSeS original washing powder body heat electric material.
7. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 6, is characterized in that simple substance Sb in described combustion synthesis method, simple substance Ag, simple substance Se, simple substance S and silver chlorate AgCl are powder.
8. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 6, the atmosphere that it is characterized in that described combustion synthesis method is vacuum or inert gas.
9. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 6, is characterized in that self propagating high temperature synthesis model or any one in the whole thermal explosion synthesis model igniting of employing one end igniting of described combustion synthesis method; The temperature that the thermal explosion synthesis model that described integral body is ignited adopts is that more than 400 ℃ the time is no more than 2min.
10. the preparation method of a kind of high-performance SbAgSeS base block thermoelectric material according to claim 2, is characterized in that the condition of described plasma activated sintering is: sintering temperature is 400-500 ℃, and sintering pressure is 20-40MPa, and temperature retention time is 5-7min.
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| CN108396217A (en) * | 2017-10-31 | 2018-08-14 | 同济大学 | A kind of high performance thermoelectric material and preparation method thereof |
| CN108767105A (en) * | 2018-05-18 | 2018-11-06 | 徐冬 | A kind of preparation method of nano composite thermoelectric materials |
| CN112374890A (en) * | 2020-11-18 | 2021-02-19 | 中国电力科学研究院有限公司 | BiAgSeS-based block thermoelectric material with nano-layered crystal grain structure and preparation method thereof |
| CN112725898A (en) * | 2020-12-18 | 2021-04-30 | 中国空间技术研究院 | Compound for thermoelectric material and preparation method thereof |
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| CN112374890A (en) * | 2020-11-18 | 2021-02-19 | 中国电力科学研究院有限公司 | BiAgSeS-based block thermoelectric material with nano-layered crystal grain structure and preparation method thereof |
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