CN102650005A - High-pressure synthesis preparation method of high-performance densification filled skutterudite thermoelectric material - Google Patents
High-pressure synthesis preparation method of high-performance densification filled skutterudite thermoelectric material Download PDFInfo
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Abstract
The invention discloses a high-pressure synthesis preparation method of a high-performance densification filled skutterudite thermoelectric material, which is characterized in comprising the following steps that 1) reaction raw materials with correspondent doses are mixed and subjected to cold press molding according to a chemical proportion for the planned synthesized filled skutterudite thermoelectric material; 2) primary high-pressure synthesizing is carried out, wherein the pressure range is 1 to 6GPa, the reaction temperature is 700 to 900 DEG C, the time is 10 to 120 minutes, the raw materials are mixed to be reacted with one another to primarily generate a transition product, and an obtained product is uniformly ground and subjected to cold press molding after being cooled and decompressed; 3) secondary high-pressure synthesizing is carried out, wherein the pressure range is 1 to 5 GPa, the reaction temperature is 550 to 650 DEG C, the time is 30 to 60 minutes, the synthesized filled shutterudite material is subjected to grinding, acidifying, drying and cold press molding after being cooled and decompressed; and 4) the final block thermoelectric material is obtained by adopting a high-pressure sintering or an electric spark discharging technology. The prepared product has high density, good mechanical machining performance and excellent thermoelectric performance, and the dimensionless thermoelectric figure of merit (ZT) is generally higher than 1. At the same time, the method and the device have simple process, take less time, save energy and have excellent industrialized production and an application prospect.
Description
Technical field
The present invention relates to the thermoelectric material field, particularly relate to a kind of high pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material.
Background technology
Present stage, global total power consumption was approximately 14TW (1TW=10
12JS
-1), wherein 80% comes from and finally discharges CO
2Oil, Sweet natural gas and coal, only account for 1% and come from carbon-free renewable and clean energy resource (underground heat, sun power, wind energy etc.).Along with the development of process of industrialization, can anticipate that the middle of this century whole world total energy consumption will reach 25-30TW.If wherein 80% consequent CO is provided by petrochemical industry and mineral fuel still
2Pollution will produce serious threat to human civilization.The novel energy economy that as soon as possible the current economy of energy that is the basis with petrochemical industry and mineral fuel is successfully carried out the transition to extensive, sustainable, low cost and environmental protection is the significant problem that current mankind society faces.At occurring in nature, clean energy resources such as sun power, underground heat are very sufficient, and how these high efficiency of energy being converted into the electric energy of being convenient to utilize at low cost just becomes the problem in science that receives much concern in the energy field.In Human's production and life process, always have lot of energy to be wasted with the form of used heat simultaneously, reducing this waste also is an important topic of energy-saving and emission-reduction.
Thermoelectric material is a kind of functional materials that can realize mutual conversion between heat energy and the electric energy.Device with thermoelectric material preparation can be realized thermo-electric generation (Seebeck effect), thus in development and use sun power and heat energy field and field of environment protection have a wide range of applications.The nondimensional thermoelectric figure of merit of thermoelectric material is defined as ZT=S
2σ T/ κ, wherein S, σ, T and κ are respectively the Seebeck coefficient of material, specific conductivity, T and thermal conductivity.Because the relatively low ZT value (being generally less than 1) of thermoelectric material, its large-scale application in field of energy conversion is restricted always.Present stage, the generating efficiency of thermo-electric device can only reach about 10% of Carnot efficiency.Exploring the effective way that improves thermoelectric material ZT value, is the research focus of present material scientific domain.
High ZT value requires material to have high as far as possible power factor S
2σ and alap thermal conductivity κ.Yet for a kind of material, be difficult to realize independent regulation and control that having optimized wherein, a performance tends to other performance deleterious impact to S, σ and κ.Such as improving the carrier concentration and the virtual mass that increases current carrier that S requires to reduce material, this will bring adverse influence to conductivity of electrolyte materials; Improve thermal conductivity (the Wiedemann-Franz law: κ that conductivity of electrolyte materials can improve the electronics contribution again
e=L σ T).In the research process of thermoelectric material, Slack has proposed the notion (CRC handbook of thermoelectrics, 1995) of " phonon glass electron crystal ", when reducing the material lattice thermal conductance, keeps higher relatively power factor.This also becomes one of research direction of the high ZT value thermoelectric material of preparation.
Skutterudite compound is a kind of middle warm area thermoelectric material, and it is the cast material (Science 1996,272,1325) of research " phonon glass electron crystal " that people such as Sales propose it.In its cage structure, fill heavy and little alkaline earth metal atom can effectively reduce the lattice thermal conductivity of material, but give the electron transport performance deleterious impact (Uher, Thermoelectrics handbook, Macro tonano, 2006) of material simultaneously.People such as Pei fill the light alkali metal atom K (Appl.Phys.Lett.2006 than the heavy ion radius that has in cage structure; 89; 221107) and Na (Appl.Phys.Lett.2009; 95,042101) improved the power factor of material significantly, but that the lattice thermal conductivity of material descends is limited.This normal pressure synthesis generally all has long characteristics (about a week) of production cycle.It is contemplated that; If can in the cage type room of tin white cobalt material, fill light and little atom; Will when effectively reducing the material lattice thermal conductivity, keep good electron transport performance, thereby find more effective approach for improving filled skutterudite material thermoelectric figure of merit ZT.
Yet use conventional atmospheric preparation method, the filling element type in the tin white cobalt material has received very big restriction, and many elements (Li, Be, Mg, Gd etc.) with small ion radius all can not be filled in the cage type room of tin white cobalt material.In addition, thermoelectric material not only need improve the ZT value of material in the large-scale application of energy field, also be unable to do without sophisticated industrialization preparation method.Use conventional atmospheric preparation method to produce filled skutterudite material time consumption and energy consumption.Appeal these problems and seriously restricted synthesizing of filled skutterudite material and development.
Summary of the invention
In order to overcome the defective of existing atmospheric preparation method; The present invention provides a kind of high pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material; Can realize the more filling of polymorphic type element in the tin white cobalt material; The filling skutterudite thermoelectric material that obtains has low thermal conductivity, high power factor, thereby effectively raises the thermoelectric figure of merit (ZT＞1) of material.
The scheme that the present invention solves aforementioned technical problem is: use pressure technique to realize the filling reaction that can not carry out under the condition of normal pressure, the filling that normal pressure can carry out down is reflected at reacts rapider under the condition of high voltage; Adopt sectional high pressure compound method, reactant mixes more even, improves the thermoelectricity capability of synthetic product; Final high-pressure sinter bulk (or the spark sintering bulk) high compaction that obtains, the machining property of filling skutterudite thermoelectric material is good.
The present invention provides a kind of high pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material, and step is following:
(1) preparation of raw material: use high-purity element simple substance as reaction raw materials, according to the stoicheiometry of the filling skutterudite thermoelectric material that fits to get the material and mix, put into mould and be cold-pressed into precast billet;
(2) the first step height is pressed into: precast billet has just been gone in the high-pressure synthesizing mould tool, under 1-6GPa, 700-900 ℃ condition, merged and initial reaction 10-120 minute, after the cooling release products therefrom ground and evenly put into mould and be cold-pressed into the transition base;
(3) second step height are pressed into: the transition base has just been gone in the high-pressure synthesizing mould tool; Reaction is 30-600 minute under 1-5GPa, 550-650 ℃ condition; The filled skutterudite material that will synthesize after the cooling release grinds evenly, residual raw materials, drying are removed in pickling, puts into mould and is cold-pressed into synthetic base;
(4) will synthesize base and sinter final block thermoelectric material into.
The present invention also provides a kind of can prepare high-performance densification filling skutterudite thermoelectric material through method of the present invention, and its thermoelectric figure of merit ZT is generally greater than 1.
Concrete preparation process is following:
1, the preparation of raw material
The present invention provides a kind of universal method for preparing filling skutterudite thermoelectric material.Every material with skutterudite crystal structure (comprise doping after material) can use the method for the invention to obtain the skutterudite thermoelectric material that element is filled.
Skutterudite thermoelectric material described in the present invention is well known to a person skilled in the art, it is meant the thermoelectric material of (skutterudite) type crystal structure that has tin white cobalt, for example CoSb
3Deng, wherein can be filled with other element alternatively.Especially, two kinds of main composition elements of skutterudite thermoelectric material of the present invention can be at least a elements that is selected from respectively in following two groups: (1) Co, Rh, Ir, Co+Fe, Co+Ni, (2) P, As, Sb, Sb+Te; Can be selected from basic metal, earth alkali metal and rare earth metal and fill element, for example Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, T1, In.
For example, high-performance densification filling skutterudite thermoelectric material of the present invention can be the binary alloy that is selected from down group: CoP
3, CoAs
3, CoSb
3, RhP
3, RhAs
3, RhSb
3, IrP
3, IrAs
3, IrSb
3Or be selected from down the group ternary alloy: CoSb
3-xTe
x(0＜x＜3), Co
1-xNi
xSb
3(0＜x＜1), Co
1-xFe
xSb
3(0＜x＜1).
The raw material set-up procedure is simple and clear: use high-purity element simple substance material as reaction raw materials, get material according to the stoicheiometry of the filling skutterudite thermoelectric material that fits to and mix, put into mould and be cold-pressed into precast billet.The used element material purity of the present invention is preferably more than 99%, more preferably greater than 99.9%, most preferably greater than 99.99% usually greater than 95%; Element material can be powder, particle, film etc.
2, the first step height is pressed into
Precast billet is put into the high-pressure synthesizing mould tool, under 1-6GPa (for example 1-5GPa), 700-900 ℃ condition, merge and initial reaction 10-120 minute (preferred 20-60 minute), release cooling back is ground and is evenly put into mould and be cold-pressed into the transition base.Selected the depending on of reaction pressure filled element effective ionic radius size, and little ionic radius is selected bigger synthesis pressure (3-6GPa) for use, and big ionic radius is selected less synthesis pressure (1-3GPa) for use; Synthesis temperature generally is higher than the fusing point of Sb.To produce thing after the cooling release and fully grind (preferably under inert gas environments such as Ar gas), initial reaction product is mixed.With products therefrom coldmoulding, get into the second step high pressure synthesis phase as the transition base.
3, the second step height is pressed into
The transition base has just been gone in the high-pressure synthesizing mould tool; Reaction 30-600 minute (preferred 60-200 minute) under 1-5GPa, 550-650 ℃ condition; The filled skutterudite material that will synthesize after the cooling release grinds evenly, residual raw materials, drying are removed in pickling, puts into mould and is cold-pressed into synthetic base.The second step high pressure synthetic temperature is a little less than the fusing point of Sb, and building-up reactions further takes place under condition of high voltage the transition base, generates the skutterudite thermoelectric material of filling.Little ionic radius is selected bigger synthesis pressure (3-5GPa) for use, and big ionic radius is selected less synthesis pressure (1-3GPa) for use.Preferably, grinding is carried out under inert gas environments such as Ar gas.
4, sintering
For example, can adopt high-pressure sinter (1GPa, 400-600 ℃, 30 minutes) or spark discharge sintering technology such as (600-700 ℃, 10-30 minute) will synthesize base and sinter final block thermoelectric material into.
The skutterudite thermoelectric material performance test methods of filling is following.
The block filling skutterudite thermoelectric material that sinters according to the requirement of experiment excision forming, is used laser perturbation thermal conductance appearance (ULVAC-RIKO TC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKO ZEM-3) thermal conductivity κ, Seebeck coefficient S and the electricalresistivity of test material respectively.
The performance evaluation of thermoelectric material mainly comprises thermal conductivity κ, Seebeck coefficient S, electricalresistivity, and the thermoelectric figure of merit ZT=S that obtains according to aforementioned physical quantity
2T/ ρ κ (wherein T is a temperature).Adopt above-mentioned preparation technology, the block thermoelectric material that is obtained has low thermal conductivity and high thermoelectric figure of merit.Thermoelectric figure of merit ZT can be higher than 1, preferably is higher than 1.5.
It should be noted that data such as the above simple substance element morphology that provides, high pressure size, temperature height, generated time are that those skilled in the art realize the present invention and the reference data and the preference data that provide for ease.In fact, because concrete operations environment and used machine equipment is different, those skilled in the art can make trickle adjustment to above-mentioned numerical range.Method of the present invention also possibly provide in the above and realize (the upper limit of for example a little higher than pressure range according to the invention, TR, time range under the operational condition outside the scope; Or be lower than the lower limit of pressure range according to the invention, TR, time range slightly); And still realizing the object of the invention at least in part, these modifications and adjustment also should be regarded as dropping within the scope of the present invention.In addition, the upper and lower limit of the numerical range that related parameter is arranged that the present invention provides can arbitrary combination, perhaps can carry out arbitrary combination with the concrete numerical value that provides among the embodiment, and the scope after the combination also is regarded as a part disclosed by the invention.
Those skilled in the art also understand; The key step of filling skutterudite thermoelectric material high pressure synthesis preparation method has only been described above; The present invention is not precluded within the possibility that also has other additional steps outside the above-mentioned key step; For example, can the block filling skutterudite thermoelectric material be carried out anneal etc. in protection of inert gas or under vacuum condition in order to eliminate the inner unrelieved stress of final block filling skutterudite thermoelectric material.
Outstanding feature of the present invention and beneficial effect:
1, technology of the present invention is simple, and reaction raw materials need not special processing, and the high pressure synthetic parameters is easy to control.
2, the high pressure compound method prepares block materials, and temperature is low, and the time is short, the energy-and time-economizing; The material density of preparation is high, and machining property is superior.
3, outstanding effect of the present invention is that prepared material generally has and is higher than 1 ZT value, and preferred value is higher than 1.5.Adopt high-performance densification filling skutterudite thermoelectric material can effectively improve the efficiency of conversion of thermo-electric device, promote thermoelectric material application in daily life.
Description of drawings
Fig. 1 is prepared sample and unfilled CoSb of embodiment 1
3The thermal conductivity of style and the relation of temperature.
Fig. 2 is prepared sample and unfilled CoSb of embodiment 1
3The resistivity of style and the relation of temperature.
Fig. 3 is prepared sample and unfilled CoSb of embodiment 1
3The Seebeck coefficient of style and the relation of temperature.
Fig. 4 is prepared sample and unfilled CoSb of embodiment 1
3The thermoelectric figure of merit ZT of style and the relation of temperature.
Fig. 5 is the thermal conductivity of the prepared sample of embodiment 2 and the relation of temperature.
Fig. 6 is the resistivity of the prepared sample of embodiment 2 and the relation of temperature.
Fig. 7 is the Seebeck coefficient of the prepared sample of embodiment 2 and the relation of temperature.
Fig. 8 is the thermoelectric figure of merit ZT of the prepared sample of embodiment 2 and the relation of temperature.
Fig. 9 is the thermal conductivity of the prepared sample of embodiment 3 and the relation of temperature.
Figure 10 is the resistivity of the prepared sample of embodiment 3 and the relation of temperature.
Figure 11 is the Seebeck coefficient of the prepared sample of embodiment 3 and the relation of temperature.
Figure 12 is the thermoelectric figure of merit ZT of the prepared sample of embodiment 3 and the relation of temperature.
Figure 13 is the thermal conductivity of the prepared sample of embodiment 4 and the relation of temperature.
Figure 14 is the resistivity of the prepared sample of embodiment 4 and the relation of temperature.
Figure 15 is the Seebeck coefficient of the prepared sample of embodiment 4 and the relation of temperature.
Figure 16 is the thermoelectric figure of merit ZT of the prepared sample of embodiment 4 and the relation of temperature.
Specifically execute real mode
In order to understand the present invention better, further set forth content of the present invention below in conjunction with accompanying drawing through embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1: high-performance densification Li fills CoSb
3The preparation method of thermoelectric material
(1) be raw material with simple substance Li (99.99%, particle), Co (99.99%, powder) and Sb (99.99%, powder), according to Li
2Co
4Sb
12Stoichiometric ratio take by weighing 8g, the mould of putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into graphite, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the first step height and be pressed into.Pressure is risen to 3GPa, be heated to about 800 ℃, heat-insulation pressure keeping 30 minutes cools off release then, takes out precast billet and fully grinds, and the mould of putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) the transition base is put into graphite, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the second step height and be pressed into.Pressure is risen to 4GPa, be heated to about 600 ℃, heat-insulation pressure keeping 180 minutes; Cool off release then, take out the transition base and fully grind, put into acid solution and remove residual raw materials; The powder drying that obtains, the mould of putting into 10.8mm is prepared into the synthetic base that thickness is 10mm on tabletting machine.
(4) will synthesize base with spark sintering method sintering 30 minutes, 680 ℃ of sintering temperatures, the Li that obtains specific density 98% fills CoSb
3Block thermoelectric material.
(5) Li is filled CoSb
3Block thermoelectric material is according to the requirement of experiment excision forming; Use laser perturbation thermal conductance appearance (ULVAC-RIKO TC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKO ZEM-3) thermal conductivity κ, Seebeck coefficient S and the electricalresistivity of test material respectively, and according to formula ZT=S
2T/ ρ κ (wherein T is a temperature) calculates its thermoelectric figure of merit ZT.Test gained data are drawn and are seen Fig. 1-Fig. 4.
Embodiment 2: high-performance densification Na fills CoSb
3The preparation method of thermoelectric material
(1) be raw material with simple substance Na (99.99%, particle), Co (99.99%, powder) and Sb (99.99%, powder), according to Na
2Co
4Sb
12Stoichiometric ratio take by weighing 8g, the mould of putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into graphite, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the first step height and be pressed into.Pressure is risen to 1GPa, be heated to about 750 ℃, heat-insulation pressure keeping 30 minutes cools off release then, takes out precast billet and fully grinds, and the mould of putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) the transition base is put into graphite, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the second step height and be pressed into.Pressure is risen to 1GPa, be heated to about 600 ℃, heat-insulation pressure keeping 180 minutes; Cool off release then, take out the transition base and fully grind, put into acid solution and remove residual raw materials; The powder drying that obtains, the mould of putting into 10.8mm is prepared into the synthetic base that thickness is 10mm on tabletting machine.
(4) will synthesize base with spark sintering method sintering 30 minutes, 680 ℃ of sintering temperatures, the Na that obtains specific density 97% fills CoSb
3Block thermoelectric material.
(5) Na is filled CoSb
3Block thermoelectric material is according to the requirement of experiment excision forming; Use laser perturbation thermal conductance appearance (ULVAC-RIKO TC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKO ZEM-3) thermal conductivity κ, Seebeck coefficient S and the electricalresistivity of test material respectively, and according to formula ZT=S
2T/ ρ κ (wherein T is a temperature) calculates its thermoelectric figure of merit ZT.Test gained data are drawn and are seen Fig. 5-Fig. 8.
Embodiment 3: high-performance densification Ca fills CoSb
3The preparation method of thermoelectric material
(1) be raw material with simple substance Ca (99.99%, powder), Co (99.99%, powder) and Sb (99.99%, powder), according to Ca
2Co
4Sb
12Stoichiometric ratio take by weighing 8g, the mould of putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into graphite, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the first step height and be pressed into.Pressure is risen to 1GPa, be heated to about 800 ℃, heat-insulation pressure keeping 30 minutes cools off release then, takes out precast billet and fully grinds, and the mould of putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) the transition base is put into China ink, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the second step height and be pressed into.Pressure is risen to 1GPa, be heated to about 600 ℃, heat-insulation pressure keeping 180 minutes; Cool off release then, take out the transition base and fully grind, put into acid solution and remove residual raw materials; The powder drying that obtains, the mould of putting into 10.8mm is prepared into the synthetic base that thickness is 10mm on tabletting machine.
(4) will synthesize base with spark sintering method sintering 30 minutes, 680 ℃ of sintering temperatures, the Ca that obtains specific density 96% fills CoSb
3Block thermoelectric material.
(5) Ca is filled CoSb
3Block thermoelectric material is according to the requirement of experiment excision forming; Use laser perturbation thermal conductance appearance (ULVAC-RIKO TC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKO ZEM-3) thermal conductivity κ, Seebeck coefficient S and the electricalresistivity of test material respectively, and according to formula ZT=S
2T/ ρ κ (wherein T is a temperature) calculates its thermoelectric figure of merit ZT.Test gained data are drawn and are seen Fig. 9-Figure 12.
Embodiment 4: high-performance densification Li and Eu dual element are filled CoSb
3The preparation method of thermoelectric material
(1) be raw material with simple substance Li (99.99%, particle), Eu (99.99%, powder), Co (99.99%, powder) and Sb (99.99%, powder), according to LiEuCo
3Sb
12Stoichiometric ratio take by weighing 8g, the mould of putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into China ink, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the first step height and be pressed into.Pressure is risen to 3GPa, be heated to about 800 ℃, heat-insulation pressure keeping 30 minutes cools off release then, takes out precast billet and fully grinds, and the mould of putting into 10.8mm is prepared into the transition base that thickness is 16mm on tabletting machine.
(3) the transition base is put into China ink, agalmatolite and boron nitride crucible and cooperate the high pressure mould of forming, in the hinge type six-plane piercer, carry out the second step height and be pressed into.Pressure is risen to 4GPa, be heated to about 600 ℃, heat-insulation pressure keeping 180 minutes; Release cooling is then taken out the transition base and is fully ground, and puts into acid solution and removes residual raw materials; The powder drying that obtains, the mould of putting into 10.8mm is prepared into the synthetic base that thickness is 10mm on tabletting machine.
(4) will synthesize base with spark sintering method sintering 30 minutes, 680 ℃ of sintering temperatures obtain the Li of specific density 98% and the CoSb of Eu dual element filling
3Block thermoelectric material.
(5) CoSb of Li and Eu dual element filling
3Block thermoelectric material is according to the requirement of experiment excision forming; Use laser perturbation thermal conductance appearance (ULVAC-RIKO TC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKO ZEM-3) thermal conductivity κ, Seebeck coefficient S and the electricalresistivity of test material respectively, and according to formula ZT=S
2T/ ρ κ (wherein T is a temperature) calculates its thermoelectric figure of merit ZT.Test gained data are drawn and are seen Figure 13-Figure 16.
Claims (11)
1. the high pressure synthesis preparation method of a high-performance densification filling skutterudite thermoelectric material said method comprising the steps of:
(1) preparation of raw material: use high-purity element simple substance as reaction raw materials, according to the stoicheiometry of the filling skutterudite thermoelectric material that fits to get the material and mix, put into mould and be cold-pressed into precast billet;
(2) the first step height is pressed into: precast billet is put into the high-pressure synthesizing mould tool, under 1-6GPa, 700-900 ℃ condition, merge and initial reaction 10-120 minute, after the release cooling products therefrom ground and evenly put into mould and be cold-pressed into the transition base;
(3) second step height are pressed into: the transition base is put into the high-pressure synthesizing mould tool; Reaction is 30-600 minute under 1-5GPa, 550-650 ℃ condition; The filled skutterudite material that will synthesize after the cooling release grinds evenly, residual raw materials, drying are removed in pickling, puts into mould and is cold-pressed into synthetic base;
(4) sintering: will synthesize base and sinter final block thermoelectric material into.
2. the high pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1; Wherein said filling skutterudite thermoelectric material is the thermoelectric material with tin white cobalt type crystal structure; Its two kinds of main composition elements are respectively at least a elements that is selected from following two groups: (1) Co, Rh, Ir, Co+Fe, Co+Ni, (2) P, As, Sb, Sb+Te; Be selected from basic metal, earth alkali metal and rare earth metal and fill element.
3. the high pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, wherein said filling skutterudite thermoelectric material are the binary alloy that is selected from down group: CoP
3, CoAs
3, CoSb
3, RhP
3, RhAs
3, RhSb
3, IrP
3, IrAs
3, IrSb
3Or be selected from down the group ternary alloy: CoSb
3-xTe
x(0＜x＜3), Co
1-xNi
xSb
3(0＜x＜1), Co
1-xFe
xSb
3(0＜x＜1); And wherein said filling element comprises in the following element one or more: Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl, In.。
4. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, wherein said filling skutterudite thermoelectric material is to fill CoSb
3
5. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, wherein the first step high pressure synthetic reaction times is 20-60 minute.
6. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, wherein the second high pressure synthetic reaction times in step was 60-200 minute.
7. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, wherein the first step height be pressed into high being pressed into of second step in grinding all under inert gas atmosphere, carry out.
8. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, the purity of wherein said element material＞95%, preferred＞99%, more preferably＞99.9%, most preferably＞99.99%.
9. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, wherein said sintering step utilizes high-pressure sinter or spark discharge sintering technology to carry out.
10. like the high pressure synthesis preparation method of each described high-performance densification filling skutterudite thermoelectric material among the claim 1-3, also be included in the annealing steps behind the sintering.
11. by the high-performance densification filling skutterudite thermoelectric material that each described method among the claim 1-10 obtains, its nondimensional thermoelectric figure of merit ZT＞1.
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| CN103924109A (en) * | 2013-11-15 | 2014-07-16 | 武汉理工大学 | New method for synthesis of super fast prepared high performance CoSb3-based thermoelectric material by self-propagating combustion |
| CN104332555A (en) * | 2014-09-15 | 2015-02-04 | 燕山大学 | Skutterudite thermoelectric material filled up with iodine, and preparation method thereof |
| CN106784280A (en) * | 2016-12-22 | 2017-05-31 | 长春理工大学 | A kind of lower thermal conductivity, high zt thermoelectric material |
| CN106784286A (en) * | 2016-12-22 | 2017-05-31 | 长春理工大学 | A kind of preparation method of lower thermal conductivity skutterudite thermoelectric material |
| CN106796980A (en) * | 2014-09-29 | 2017-05-31 | 株式会社Lg化学 | Compound semiconductor and preparation method thereof |
| CN108767105A (en) * | 2018-05-18 | 2018-11-06 | 徐冬 | A kind of preparation method of nano composite thermoelectric materials |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103924109A (en) * | 2013-11-15 | 2014-07-16 | 武汉理工大学 | New method for synthesis of super fast prepared high performance CoSb3-based thermoelectric material by self-propagating combustion |
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| CN104332555A (en) * | 2014-09-15 | 2015-02-04 | 燕山大学 | Skutterudite thermoelectric material filled up with iodine, and preparation method thereof |
| CN106796980A (en) * | 2014-09-29 | 2017-05-31 | 株式会社Lg化学 | Compound semiconductor and preparation method thereof |
| CN106796980B (en) * | 2014-09-29 | 2018-11-23 | 株式会社Lg化学 | Compound semiconductor and preparation method thereof |
| CN106784280A (en) * | 2016-12-22 | 2017-05-31 | 长春理工大学 | A kind of lower thermal conductivity, high zt thermoelectric material |
| CN106784286A (en) * | 2016-12-22 | 2017-05-31 | 长春理工大学 | A kind of preparation method of lower thermal conductivity skutterudite thermoelectric material |
| CN108767105A (en) * | 2018-05-18 | 2018-11-06 | 徐冬 | A kind of preparation method of nano composite thermoelectric materials |
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| CN102650005B (en) | 2015-11-25 |
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