CN103107279B - High-temperature thermoelectric material and preparation method thereof - Google Patents
High-temperature thermoelectric material and preparation method thereof Download PDFInfo
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- CN103107279B CN103107279B CN201310057168.1A CN201310057168A CN103107279B CN 103107279 B CN103107279 B CN 103107279B CN 201310057168 A CN201310057168 A CN 201310057168A CN 103107279 B CN103107279 B CN 103107279B
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Abstract
The invention relates to high-temperature thermoelectric material and a preparation method thereof. The high-temperature thermoelectric material has a general formula: Ca2-xRExAg2-ySb2, wherein La or Ce or Pr or Nd or Sm is adopted for the RE, the X is smaller than or equal to 1, and the y is smaller than or equal to 1; the raw materials are heated to 1100 DEG C till a decomposition point and a melting point do not exist; polycrystal materials are prepared by using a high temperature solid state method or a metal co-solvent method, and prepared and molded through spark plasma sintering (SPS); and as for thermoelectric property of an obtained block of the materials, the thermoelectric figure of merit can reach to 0.67 in 1100K. By means of the preparation method, the obtained high-temperature thermoelectric polycrystal block which is high in purity, high in efficiency and capable of existing in the air stably is prepared, and can be used as high-temperature thermoelectric materials.
Description
Technical field
The present invention relates to thermoelectric material of a kind of high temperature application and preparation method thereof, particularly Ca
2-xrE
xag
2-ysb
2(RE=La, Ce, Pr, Nd, Sm) material and preparation method, belong to new energy materials field.
Background technology
Thermoelectric material refers to the semiconducting compound that a class is special, utilizes the mutual conversion that this kind of material people can realize between heat energy and electric energy easily.In other words, by this medium of thermoelectric material, we can impose temperature difference to produce electric energy at two ends, meanwhile, also can impose voltage at two ends thus produce temperature difference.This physical characteristic of thermoelectric material makes it in generating and refrigeration, have this great application prospect, particularly in energy-saving and emission-reduction, by the available electric energy of thermal power transfer that will discard, can greatly improve current energy use efficiency, and slow down the greenhouse effect caused because of combustion of fossil fuels.These available waste heat comprise vehicle exhaust heat, the discarded heat of industrial production and residential houses.Meanwhile, based on the refrigeration device of thermoelectric material due to not containing mechanical pump movable part, therefore more quiet reliable, the processing of various sizes can be carried out, especially applicable small, reliably, the application of portable refrigerating device.
The thermoelectric material (be commonly referred to as and be greater than 1000K) of high temperature application has very important application prospect in the field such as Aero-Space, Waste Heat Recovery.Currently mainly contain two kinds: Si in the higher high-temperature thermoelectric material having obtained certain applications of high-temperature region efficiency
x-Ge
yalloy and Yb
14mnSb
11, but this two classes material has problems separately, and one is Si
x-Ge
yalloy efficiency is not high, and its p-type device at high temperature only has the efficiency of thermoelectric figure of merit (zT=0.6); Two is Yb
14mnSb
11responsive in atmosphere, material is difficult to preparation, element manufacturing difficulty.Above-mentioned Problems existing limits its application.See Wood, C.Energy Con VersionManage.1984,24,331.2. and Brown, S.R.; Kauzlarich, S.M.; Gascoin, F.; Snyder, G.J.Chem.Mater.2006,18,1873..
Summary of the invention
For the deficiency of current high-temperature thermoelectric material technology, the invention provides a kind of thermoelectric material that can be applicable to hot conditions.Present invention also offers the preparation method and application of described thermoelectric material.
Technical scheme of the present invention is as follows:
A kind of high-temperature thermoelectric material, has general formula Ca
2-xrE
xag
2-ysb
2, RE=La, Ce, Pr, Nd or Sm, x≤1, y≤1; Be heated to 1100 DEG C without decomposition point and fusing point;
Described Ca
2-xrE
xag
2-ysb
2(RE=La, Ce, Pr, Nd, Sm) material is stable in the air.
Described Ca
2-xrE
xag
2-ysb
2(RE=La, Ce, Pr, Nd, Sm) material belongs to hexagonal crystal system, P6
3mc space group.
Preferred according to the present invention, described high-temperature thermoelectric material is one of following:
Ca
2-xCe
xAg
2-ySb
2(x=0.33,y=0.31)，Ca
2-xLa
xAg
2-ySb
2(x=0.18,y=0.15)，Ca
2-xPr
xAg
2-ySb
2(x=0.26,y=0.30)，Ca
2-xNd
xAg
2-ySb
2(x=0.28,y=0.27)，Ca
2-xSm
xAg
2-ySb
2(x=0.32,y=0.35)。
High-temperature thermoelectric material of the present invention, adopts the metal simple-substance in composition to be that raw material obtains polycrystal material by high temperature solid state reaction or metal promoted solvent method, and by plasma discharging (SPS) sinter molding.
The preparation of high-temperature thermoelectric material of the present invention can adopt high-temperature solid phase preparation method, also can adopt metal promoted solvent preparation.Below be described respectively.
One, high-temperature solid phase preparation method
According to the present invention, a kind of preparation method of high-temperature thermoelectric material, comprises step as follows:
(1) raw material adopts metal simple-substance: Ag(silver), Sb(antimony), Ca(calcium) and, RE; RE is selected from La(lanthanum), Ce(cerium), Pr(praseodymium) and, Nd(neodymium) or Sm(samarium).
According to Ca
2-xrE
xag
2-ysb
2stoichiometric proportion batching.The raw material prepared is put into niobium (Nb) pipe, and niobium pipe is sealed by High Temperature Argon arc-welding in glove box.
(2) niobium pipe is enclosed in quartz ampoule, vacuumize, then quartz ampoule is put into tube furnace, be warming up to 1100 DEG C-1150 DEG C by 200-250 DEG C/h, and at 1100 DEG C-1150 DEG C insulation 72-100 hour, close body of heater power supply, Temperature fall is to room temperature;
(3) niobium pipe is opened in glove box, the raw material that step (2) processes fully is ground, reload niobium pipe, to be encapsulated into again in quartz ampoule and to vacuumize, quartz ampoule being put into tube furnace, is warming up to 1100 DEG C-1150 DEG C by 200-250 DEG C/h, and at 1100 DEG C-1150 DEG C insulation 40-48 hour, close body of heater power supply, body of heater cools naturally, cools to room temperature; Obtain pure phase polycrystal material.
(4) the pure phase polycrystal material obtained fully is ground, puts into graphite grinding tool, by plasma discharging (SPS) sintering, 1100 DEG C-1150 DEG C, obtain fine and close polycrystalline bulk under 30-40MPa.
Two, metal promoted solvent preparation
According to the present invention, a kind of preparation method of high-temperature thermoelectric material, comprises step as follows:
1. raw material adopts metal simple-substance: Ag(silver), Sb(antimony), Ca(calcium) and, RE; RE is selected from La(lanthanum), Ce(cerium), Pr(praseodymium) and, Nd(neodymium) or Sm(samarium); According to Ca/RE/Ag/Sb=1:1:1:2 molar ratio ingredient, then add metal promoted solvent and fully mix, Ca: metal promoted solvent=1:10-20 mol ratio;
2. compound is put into alumina crucible, again alumina crucible is enclosed quartz ampoule, quartz ampoule is put into box type furnace, 800 DEG C-900 DEG C are warming up to by 200-250 DEG C/h, and at 800 DEG C-900 DEG C insulation 24-48 hour, then cool to 500 DEG C-600 DEG C through 3-10 DEG C/h, and at 500 DEG C-600 DEG C insulation 24-48 hour, remove metal promoted solvent; Obtain polycrystal material.
3. the polycrystal material obtained fully is ground, puts into graphite grinding tool, by plasma discharging (SPS) sintering, 1100 DEG C-1150 DEG C, obtain fine and close polycrystalline block or sheet under 30-40MPa.
Preferred according to the present invention, described flux is metallic lead (Pb).
The method removes metal promoted separated from solvent by high temperature centrifugal process to go out clean polycrystal material.
The present invention by constitutive material according to 2-x:x:2-y:2 (x≤1, y≤1) batching, pure phase polycrystal raw material is obtained by high temperature two-step reaction method or metal promoted solvent method, and by SPS(discharge plasma sintering) prepare shaping, high-purity, high efficiency high temperature thermoelectric polycrystalline bulk can be obtained.Material C a of the present invention
2-xce
xag
2-ysb
2show when high temperature 1100 DEG C without decomposition point and fusing point through the test of TG-DSC thermal analyses.Wherein to Ca
2-xce
xag
2-ysb
2carry out thermoelectric property test result after (x=0.33, y=0.31) sample cuts and show have when high temperature 1100K the thermoelectric figure of merit being greater than zT=0.67, can be used as high-temperature thermoelectric material application.For generating and refrigerating field.
Ca of the present invention
2-xce
xag
2-ysb
2high temperature thermoelectric crystalline material, under high temperature 1100K, have the thermoelectric figure of merit of zT=0.67, efficiency is high; And Ca
2-xce
xag
2-ysb
2high temperature thermoelectric crystalline material is stable in the air, is convenient to preparation, and crystal is easy to cutting, and making devices is easy.
Accompanying drawing explanation
Fig. 1 high-temperature thermoelectric material Ca
2-xrE
xag
2-ysb
2(RE=La, Ce, Pr, Nd or Sm) crystal structure schematic diagram, wherein black ball represents Sb, and grey chromosphere represents Ag, and the large ball of white represents Ca and rare earth RE occupies same position.
Fig. 2 is the Ca of embodiment 2
2-xce
xag
2-ysb
2(x=0.33, y=0.31) thermal analyses result schematic diagram.
Fig. 3 is the Ca of embodiment 1
2-xce
xag
2-ysb
2the Polycrystalline sheet obtained after (x=0.33, y=0.31) is shaping by SPS.
Fig. 4 is the Ca of embodiment 1
2-xce
xag
2-ysb
2the SEM microphoto of the Polycrystalline sheet section obtained after (x=0.33, y=0.31) is shaping by SPS.
Fig. 5 is the Ca of embodiment 2
2-xce
xag
2-ysb
2the block thermoelectric property test result that (x=0.33, y=0.31) obtains.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but do not limit therewith.
Embodiment 1, high-temperature thermoelectric material Ca
2-xce
xag
2-ysb
2(x=0.33, y=0.31) metal fusing agent preparation method:
Raw material adopts metal simple-substance: Ca(calcium), Ce(cerium), Ag(silver) and, Sb(antimony), according to Ca/RE/Ag/Sb=1:1:1:2 molar ratio ingredient, then add metal Pb cosolvent and fully mix, Ca:Pb=1:20 mol ratio; Obtain compound.
First the compound prepared is put into corundum crucible, and put into quartz ampoule to vacuumize, box type furnace is put in the reaction of sealing, 250 DEG C/h is warming up to 900 DEG C, and 900 DEG C of insulations 24 hours, then slow 5 DEG C/h was cooled to 600 DEG C, and now remove flux at 600 DEG C of insulation 24h, by low speed centrifuge 2500r/min centrifugal 5 minutes, it was hexagonal crystal system, P6 that the polycrystal material obtained measures crystal structure by single crystal diffraction method
3mc space group, diffraction patterns shows the crystal structure had as shown in Figure 1.By the polycrystal material obtained by plasma discharging (SPS) 1100 DEG C, 40MPa is shaping obtains dense multicrystalline sheet.As shown in Figure 3, Figure 4.
Embodiment 2, series of high temperature thermoelectric material Ca
2-xce
xag
2-ysb
2(x=0.33, y=0.31) high-temperature solid phase preparation method:
Constitutive material metal simple-substance Ca/Ce/Ag/Sb is put into metal niobium pipe according to stoichiometric proportion (1.67:0.33:1.69:2), obtains pure phase raw material by two-step reaction process.Nb pipe is enclosed quartz ampoule by the first step, vacuumizes, quartz ampoule is put into tube furnace 250 DEG C/h and be warming up to 1100 DEG C, and 1100 DEG C of insulations 96 hours, now closes body of heater power supply fast cooling to room temperature; Niobium pipe is opened by second step in glove box, raw material is fully ground and reloads niobium pipe, and to be encapsulated into again in quartz ampoule and to vacuumize, quartz ampoule is put into tube furnace 250 DEG C/h and be warming up to 1100 DEG C, and 1100 DEG C of insulations 48 hours, now close body of heater power supply fast cooling to room temperature, the pure phase polycrystal raw material obtained fully is ground, and put into graphite grinding tool, by discharge plasma sintering 1100 DEG C, obtain fine and close polycrystalline bulk under 40MPa.
Get the Polycrystalline after densification and carry out thermal analyses, obtain result as shown in Figure 2, this material at high temperature stablize, until 1100 DEG C all without decomposition point without fusing point, carry out after sample is cut thermoelectric property test obtain result as shown in Figure 5: can 0.67 be reached at 1100K thermoelectric figure of merit.
Embodiment 3, high-temperature thermoelectric material Ca
2-xla
xag
2-ysb
2(x=0.18, y=0.15) high-temperature solid phase preparation method:
As described in Example 2, difference is: four kinds of simple substance raw materials load in metal niobium pipe by the molar ratio of Ca:La:Ag:Sb=1.82:0.18:1.85:2, other step and technological parameter all identical with embodiment 2.
Embodiment 4, high-temperature thermoelectric material Ca
2-xpr
xag
2-ysb
2(x=0.26, y=0.30) high-temperature solid phase preparation method:
As described in Example 2, difference is: four kinds of simple substance raw materials load in metal niobium pipe by the molar ratio of Ca:Pr:Ag:Sb=1.74:0.26:1.70:2, other step and technological parameter all identical with embodiment 2.
Embodiment 5, high-temperature thermoelectric material Ca
2-xnd
xag
2-ysb
2(x=0.28, y=0.27) high-temperature solid phase preparation method:
As described in Example 2, difference is: four kinds of simple substance raw materials load in metal niobium pipe by the molar ratio of Ca:Nd:Ag:Sb=1.72:0.28:1.73:2, other step and technological parameter all identical with embodiment 2.
Embodiment 6, high-temperature thermoelectric material Ca
2-xsm
xag
2-ysb
2(x=0.32, y=0.35) high-temperature solid phase preparation method:
As described in Example 2, difference is: four kinds of simple substance raw materials load in metal niobium pipe by the molar ratio of Ca:Sm:Ag:Sb=1.68:0.32:1.65:2, other step and technological parameter all identical with embodiment 2.
Claims (4)
1. a high-temperature thermoelectric material, has general formula Ca
2-xrE
xag
2-ysb
2, RE=La, Ce, Pr, Nd or Sm, x≤1, y≤1; Be heated to 1100 DEG C without decomposition point and fusing point; This material is one of following:
Ca
2-xCe
xAg
2-ySb
2，x=0.33,y=0.31，
Ca
2-xLa
xAg
2-ySb
2，x=0.18,y=0.15，
Ca
2-xPr
xAg
2-ySb
2，x=0.26,y=0.30，
Ca
2-xNd
xAg
2-ySb
2 ，x=0.28, y=0.27，
Ca
2-xSm
xAg
2-ySb
2，x=0.32,y=0.35。
2. the preparation method of high-temperature thermoelectric material according to claim 1, comprises step as follows:
(1) raw material adopts metal simple-substance: Ag, Sb, Ca, RE; RE is selected from La, Ce, Pr, Nd or Sm; According to Ca
2-xrE
xag
2-ysb
2stoichiometric proportion batching; The raw material prepared is put into niobium pipe, and niobium pipe is sealed by High Temperature Argon arc-welding in glove box;
(2) niobium pipe is enclosed in quartz ampoule, vacuumize, then quartz ampoule is put into tube furnace, be warming up to 1100 DEG C-1150 DEG C by 200-250 DEG C/h, and at 1100 DEG C-1150 DEG C insulation 72-100 hour, close body of heater power supply, Temperature fall is to room temperature;
(3) niobium pipe is opened in glove box, the raw material that step (2) processes fully is ground, reload niobium pipe, to be encapsulated into again in quartz ampoule and to vacuumize, quartz ampoule being put into tube furnace, is warming up to 1100 DEG C-1150 DEG C by 200-250 DEG C/h, and at 1100 DEG C-1150 DEG C insulation 40-48 hour, close body of heater power supply, body of heater cools naturally, cools to room temperature; Obtain pure phase polycrystal material;
(4) the pure phase polycrystal material obtained fully is ground, puts into graphite grinding tool, by discharge plasma sintering, 1100 DEG C-1150 DEG C, obtain fine and close polycrystalline bulk under 30-40MPa.
3. the preparation method of high-temperature thermoelectric material according to claim 1, comprises step as follows:
1. raw material adopts metal simple-substance: Ag, Sb, Ca, RE; RE is selected from La, Ce, Pr, Nd or Sm; According to Ca/RE/Ag/Sb=1:1:1:2 molar ratio ingredient, then add metal fusing agent and fully mix, Ca: metal fusing agent=1:10-20 mol ratio;
2. compound is put into alumina crucible, again alumina crucible is enclosed quartz ampoule, quartz ampoule is put into box type furnace, 800 DEG C-900 DEG C are warming up to by 200-250 DEG C/h, and at 800 DEG C-900 DEG C insulation 24-48 hour, then cool to 500 DEG C-600 DEG C through 3-10 DEG C/h, and at 500 DEG C-600 DEG C insulation 24-48 hour, remove metal fusing agent; Obtain polycrystal material;
3. the polycrystal material obtained fully is ground, puts into graphite grinding tool, by discharge plasma sintering, 1100 DEG C-1150 DEG C, obtain fine and close polycrystalline block or sheet under 30-40MPa.
4. the preparation method of high-temperature thermoelectric material as claimed in claim 3, wherein said flux is metallic lead.
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| CN107946448B (en) * | 2017-11-24 | 2019-08-30 | 山东大学 | A kind of high-temperature thermoelectric material Ca (Zn of the high figure of merit(1-x)/2/Agx-σ) Sb and preparation method thereof |
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Non-Patent Citations (1)
| Title |
|---|
| F.Merlo, M. pani, M. L.Fornasini.RMX compounds formed by alkaline earths, europium and ytterbium-I. Ternary phases with M=Cu,Ag,Au;X=Sb,Bi.《Journal of the Less-Common Metals》.1990,(第166期),Page 319-327. * |
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