CN102650005B - The high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material - Google Patents
The high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material Download PDFInfo
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Abstract
The present invention discloses a kind of high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material, it is characterized in that: 1) according to the stoicheiometry of the filling skutterudite thermoelectric material fitted to, and gets the reaction raw materials mixing also coldmoulding of corresponding dosage; 2) the first step high-pressure synthesis, pressure range 1-6GPa, temperature of reaction 700-900 DEG C, time 10-120 minute, merges raw material and initial reaction generates transiting product, is ground evenly and coldmoulding by products therefrom after cooling release; 3) second step high-pressure synthesis, pressure range 1-5Gp, temperature of reaction 550-650 DEG C, time 30-600 minute, after cooling release by synthesize filled skutterudite ground material, pickling, drying, and coldmoulding; 4) adopt high-pressure sinter or spark sintering technology, obtain final block thermoelectric material.Products therefrom density is high, and have good machining property, thermoelectricity capability is superior, and zero dimension thermoelectric figure of merit (ZT) is general higher than 1, and present invention process is simple simultaneously, and consuming time short, save energy, has excellent industrialization production and application prospect.
Description
Technical field
The present invention relates to 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, and come from carbon-free renewable and clean energy resource (underground heat, sun power, wind energy etc.) and only account for 1%.Along with the development of process of industrialization, it is expected to the middle of this century whole world total energy consumption will reach 25-30TW.If wherein 80% is still provided by petrochemical industry and mineral fuel, consequent CO
2pollution will produce serious threat to human civilization.The significant problem that current mankind society faces by current economy of energy successful transition based on petrochemical industry and mineral fuel to the novel energy economy of extensive, sustainable, low cost and environmental protection as soon as possible.At occurring in nature, the clean energy such as sun power, underground heat resource is very sufficient, and how these high efficiency of energy being converted into the electric energy being convenient to utilize at low cost just becomes the problem in science received much concern in energy field.Simultaneously in the production and life process of the mankind, always there is a large amount of energy to be wasted with the form of used heat, reduce the important topic that this waste is also energy-saving and emission-reduction.
Thermoelectric material is a kind of functional materials that can realize conversion mutually between heat energy and electric energy.The device prepared with thermoelectric material can realize thermo-electric generation (Seebeck effect), thus has a wide range of applications at exploitation sun power and heat energy field and field of environment protection.The nondimensional thermoelectric figure of merit of thermoelectric material is defined as ZT=S
2σ T/ κ, wherein S, σ, T and κ are the Seebeck coefficient of material, specific conductivity, absolute temperature and thermal conductivity respectively.Due to the ZT value (being generally less than 1) that thermoelectric material is relatively low, it is restricted in the large-scale application of field of energy conversion always.Present stage, the generating efficiency of thermo-electric device can only reach about 10% of Carnot efficiency.Exploring the effective way improving thermoelectric material ZT value, is the study hotspot of present material scientific domain.
High ZT value requires that material has power factor S high as far as possible
2σ and alap thermal conductivity κ.But for a kind of material, be difficult to realize the independent regulation and control to S, σ and κ, optimize a wherein performance and often disadvantageous effect is brought to other performances.Such as improve S require to reduce the carrier concentration of material and increase the virtual mass of current carrier, this brings adverse influence will to the specific conductivity of material; The specific conductivity improving material can improve again thermal conductivity (the Wiedemann-Franz law: κ of electronics contribution
e=L σ T).In the research process of thermoelectric material, the concept (CRChandbookofthermoelectrics, 1995) that Slack proposes " phonon glasses electron crystal ", keeps relatively high power factor while reducing material lattice thermal conductance.This also becomes one of important research direction of preparation high zt thermoelectric material.
Skutterudite compound is warm area thermoelectric material in one, and the people such as Sales propose the cast material (Science1996,272,1325) that it is research " phonon glasses electron crystal ".The lattice thermal conductivity that heavy and little alkaline earth metal atom can effectively reduce material is filled in its cage structure, bring disadvantageous effect (Uher but to the electron transport performance of material simultaneously, Thermoelectricshandbook, Macrotonano, 2006).The people such as Pei fill the light alkali metal atom K (Appl.Phys.Lett.2006 had compared with heavy ion radius in cage structure, 89,221107) and Na (Appl.Phys.Lett.2009,95,042101) improve the power factor of material significantly, but the decline of the lattice thermal conductivity of material is limited.This normal pressure synthesis generally all has the feature (about a week) of production cycle length.It is contemplated that, if light and little atom can be filled in the cage type room of tin white cobalt material, excellent electron transport performance will be kept while effectively reducing material lattice thermal conductivity, thus find more effective approach for improving filled skutterudite material thermoelectric figure of merit ZT.
But using conventional atmospheric preparation method, the filling element type in tin white cobalt material is limited by very large, and many elements (Li, Be, Mg, Gd etc.) with small ionic radii all can not be filled in the cage type room of tin white cobalt material.In addition, thermoelectric material not only needs in the large-scale application of energy field the ZT value improving material, also be unable to do without ripe industrialization preparation method.Conventional atmospheric preparation method is used to produce filled skutterudite material time consumption and energy consumption.Appeal synthesis and development that these problems seriously constrain filled skutterudite material.
Summary of the invention
In order to overcome the defect of existing atmospheric preparation method, the invention provides a kind of high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material, the filling of more polymorphic type element in tin white cobalt material can be realized, the filling skutterudite thermoelectric material obtained has low thermal conductivity, high power factor, thus effectively raises the thermoelectric figure of merit (ZT > 1) of material.
The scheme that the present invention solves aforementioned technical problem is: the filling reaction can not carried out under using pressure technique to realize condition of normal pressure, and the filling can carried out under normal pressure reaction reacts rapider under elevated pressure conditions; Adopt sectional type high pressure synthesis method, reactant mixing evenly, improve the thermoelectricity capability of synthetic product; High-pressure sinter bulk (or the spark sintering bulk) high compaction of final acquisition, the machining property of filling skutterudite thermoelectric material is excellent.
The invention provides a kind of high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material, step is as follows:
(1) preparation of raw material: use high-purity element simple substance as reaction raw materials, according to the filling skutterudite thermoelectric material fitted to stoicheiometry feeding and mix, put into mould and be cold-pressed into precast billet;
(2) the first step high-pressure synthesis: precast billet just entered in high-pressure synthesis mould, merges and initial reaction 10-120 minute under the condition of 1-6GPa, 700-900 DEG C, after cooling release, mould is evenly put in products therefrom grinding and is cold-pressed into transition base;
(3) second step high-pressure synthesis: transition base has just been entered in high-pressure synthesis mould, 30-600 minute is reacted under the condition of 1-5GPa, 550-650 DEG C, by even for the filled skutterudite ground material synthesized, pickling removing residual raw materials, drying after cooling release, put into mould and be cold-pressed into synthesis base;
(4) synthesis base is sintered into final block thermoelectric material.
Present invention also offers one and prepare high-performance densification filling skutterudite thermoelectric material by method of the present invention, its thermoelectric figure of merit ZT is generally greater than 1.
Concrete preparation process is as follows:
1, the preparation of raw material
The invention provides a kind of universal method preparing filling skutterudite thermoelectric material.Every material (comprising the material after doping) with skutterudite crystal structure, can use the method for the invention to obtain the skutterudite thermoelectric material of element filling.
Skutterudite thermoelectric material described in the present invention well known to a person skilled in the art, it refers to the thermoelectric material with tin white cobalt (skutterudite) type crystal structure, such as 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 selected from least one element in following two groups respectively: (1) Co, Rh, Ir, Co+Fe, Co+Ni, (2) P, As, Sb, Sb+Te; And fill element and can be selected from basic metal, alkaline-earth metal and rare earth metal, such as 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.
Such as, high-performance densification filling skutterudite thermoelectric material of the present invention can be selected from the binary alloy of lower group: CoP
3, CoAs
3, CoSb
3, RhP
3, RhAs
3, RhSb
3, IrP
3, IrAs
3, IrSb
3; Or be selected from the ternary alloy of lower group: CoSb
3-xte
x(0 < x < 3), Co
1-xni
xsb
3(0 < x < 1), Co
1-xfe
xsb
3(0 < x < 1).
Raw material set-up procedure is simple and clear: use high-purity element simple substance material as reaction raw materials, mixes, put into mould and be cold-pressed into precast billet according to the stoicheiometry feeding of the filling skutterudite thermoelectric material fitted to.The present invention's element material purity used is greater than 95% usually, is preferably more than 99%, is more preferably greater than 99.9%, be most preferably greater than 99.99%; Element material can be powder, particle, film etc.
2, the first step high-pressure synthesis
Precast billet is put into high-pressure synthesis mould, merge and initial reaction 10-120 minute (preferred 20-60 minute) under the condition of 1-6GPa (such as 1-5GPa), 700-900 DEG C, after release cooling, grinding is evenly put into mould and is cold-pressed into transition base.Selected the depending on of reaction pressure fills element effective ionic radius size, and little ionic radius selects larger synthesis pressure (3-6GPa), the synthesis pressure (1-3GPa) of large ionic radius selection of small; Synthesis temperature is generally higher than the fusing point of Sb.After cooling release, production thing is fully ground (preferably under the inert gas environments such as Ar gas), initial reaction product is mixed.By products therefrom coldmoulding, enter the second step high-pressure synthesis stage as transition base.
3, second step high-pressure synthesis
Transition base is just entered in high-pressure synthesis mould, react under the condition of 1-5GPa, 550-650 DEG C 30-600 minute (preferred 60-200 minute), by even for the filled skutterudite ground material synthesized, pickling removing residual raw materials, drying after cooling release, put into mould and be cold-pressed into synthesis base.The temperature of second step high-pressure synthesis is a little less than the fusing point of Sb, and transition base further building-up reactions occurs under elevated pressure conditions, generates the skutterudite thermoelectric material of filling.Little ionic radius selects larger synthesis pressure (3-5GPa), the synthesis pressure (1-3GPa) of large ionic radius selection of small.Preferably, grind and carry out under the inert gas environments such as Ar gas.
4, sinter
Such as, the technology such as high-pressure sinter (1GPa, 400-600 DEG C, 30 minutes) or spark sintering (600-700 DEG C, 10-30 minute) can be adopted to sinter synthesis base into final block thermoelectric material.
The skutterudite thermoelectric material performance test methods of filling is as follows.
By the block filling skutterudite thermoelectric material that sinters according to requirement of experiment excision forming, laser perturbation thermal conductance instrument (ULVAC-RIKOTC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKOZEM-3) is used to distinguish thermal conductivity κ, Seebeck coefficient S and the electricalresistivityρ of test material.
The performance evaluation of thermoelectric material mainly comprises thermal conductivity κ, Seebeck coefficient S, electricalresistivityρ, and according to the thermoelectric figure of merit ZT=S that said physical measures
2t/ ρ κ (wherein T is temperature).Adopt above-mentioned preparation technology, the block thermoelectric material obtained has low thermal conductivity and high thermoelectric figure of merit.Thermoelectric figure of merit ZT can higher than 1, preferably higher than 1.5.
It should be noted that the above data such as simple substance element morphology, high pressure size, temperature height, generated time provided are that conveniently those skilled in the art realize the present invention and the reference data provided and preference data.In fact, due to the difference of concrete operations environment and used machine equipment, those skilled in the art can make trickle adjustment to above-mentioned numerical range.Method of the present invention realizes (the such as upper limit of a little higher than pressure range of the present invention, temperature range, time range also may provide the operational condition outside scope above under, or slightly lower than the lower limit of pressure range of the present invention, temperature range, time range), and still realizing object of the present invention at least in part, these amendments and adjustment also should be considered as falling within the scope of the present invention.In addition, the upper and lower limit of the numerical range of the relevant parameters that the present invention provides can arbitrary combination, or can carry out arbitrary combination with the concrete numerical value that provides in embodiment, and the scope after combination is also considered as a part disclosed by the invention.
Those skilled in the art also understand; foregoing describes only the key step of filling skutterudite thermoelectric material high-pressure synthesis preparation method; the present invention is not precluded within the possibility that also there are other additional steps outside above-mentioned key step; such as in order to eliminate the unrelieved stress of final block filling skutterudite thermoelectric material inside, can by block filling skutterudite thermoelectric material in protection of inert gas or carry out anneal etc. under vacuum.
Outstanding feature of the present invention and beneficial effect:
1, present invention process is simple, and reaction raw materials is without the need to special process, and high-pressure synthesis parameter is easy to control.
2, high pressure synthesis method prepares block materials, and temperature is low, and the time is short, energy-and time-economizing; The material density of preparation is high, and machining property is superior.
3, outstanding effect of the present invention is the ZT value that prepared material generally has higher than 1, and preferred value is higher than 1.5.Adopt high-performance densification filling skutterudite thermoelectric material effectively can improve the efficiency of conversion of thermo-electric device, promote thermoelectric material application in daily life.
Accompanying drawing explanation
The sample of Fig. 1 prepared by embodiment 1 and unfilled CoSb
3the thermal conductivity of style and the relation of temperature.
The sample of Fig. 2 prepared by embodiment 1 and unfilled CoSb
3the resistivity of style and the relation of temperature.
The sample of Fig. 3 prepared by embodiment 1 and unfilled CoSb
3the Seebeck coefficient of style and the relation of temperature.
The sample of Fig. 4 prepared by embodiment 1 and unfilled CoSb
3the thermoelectric figure of merit ZT of style and the relation of temperature.
The thermal conductivity of sample of Fig. 5 prepared by embodiment 2 and the relation of temperature.
The resistivity of sample of Fig. 6 prepared by embodiment 2 and the relation of temperature.
The Seebeck coefficient of sample of Fig. 7 prepared by embodiment 2 and the relation of temperature.
The thermoelectric figure of merit ZT of the sample of Fig. 8 prepared by embodiment 2 and the relation of temperature.
The thermal conductivity of sample of Fig. 9 prepared by embodiment 3 and the relation of temperature.
The resistivity of sample of Figure 10 prepared by embodiment 3 and the relation of temperature.
The Seebeck coefficient of sample of Figure 11 prepared by embodiment 3 and the relation of temperature.
The thermoelectric figure of merit ZT of the sample of Figure 12 prepared by embodiment 3 and the relation of temperature.
The thermal conductivity of sample of Figure 13 prepared by embodiment 4 and the relation of temperature.
The resistivity of sample of Figure 14 prepared by embodiment 4 and the relation of temperature.
The Seebeck coefficient of sample of Figure 15 prepared by embodiment 4 and the relation of temperature.
The thermoelectric figure of merit ZT of the sample of Figure 16 prepared by embodiment 4 and the relation of temperature.
Specifically execute real mode
In order to understand the present invention better, set forth content of the present invention below in conjunction with accompanying drawing further by embodiment, but content of the present invention is not only confined to embodiment below.
Embodiment 1: high-performance densification Li fills CoSb
3the preparation method of thermoelectric material
(1) with simple substance Li (99.99%, particle), Co (99.99%, powder) and Sb (99.99%, powder) for raw material, according to Li
2co
4sb
12stoichiometric ratio take 8g, the mould putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into the Belt-type tools that graphite, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out the first step high-pressure synthesis.Pressure is risen to 3GPa, is heated to about 800 DEG C, heat-insulation pressure keeping 30 minutes, then cools release, and take out precast billet and fully grind, the mould putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) transition base is put into the Belt-type tools that graphite, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out second step high-pressure synthesis.Pressure is risen to 4GPa, is heated to about 600 DEG C, heat-insulation pressure keeping 180 minutes, then cool release, take out transition base and fully grind, put into acid solution and remove residual raw materials, the powder drying obtained, the mould putting into 10.8mm is prepared into the synthesis base that thickness is 10mm on tabletting machine.
(4) synthesis base spark sintering method is sintered 30 minutes, sintering temperature 680 DEG C, the Li obtaining relative density 98% fills CoSb
3block thermoelectric material.
(5) Li is filled CoSb
3block thermoelectric material is according to requirement of experiment excision forming, use thermal conductivity κ, Seebeck coefficient S and the electricalresistivityρ of laser perturbation thermal conductance instrument (ULVAC-RIKOTC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKOZEM-3) difference test material, and according to formula ZT=S
2t/ ρ κ (wherein T is temperature) calculates its thermoelectric figure of merit ZT.Test the data obtained is drawn and is seen Fig. 1-Fig. 4.
Embodiment 2: high-performance densification Na fills CoSb
3the preparation method of thermoelectric material
(1) with simple substance Na (99.99%, particle), Co (99.99%, powder) and Sb (99.99%, powder) for raw material, according to Na
2co
4sb
12stoichiometric ratio take 8g, the mould putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into the Belt-type tools that graphite, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out the first step high-pressure synthesis.Pressure is risen to 1GPa, is heated to about 750 DEG C, heat-insulation pressure keeping 30 minutes, then cools release, and take out precast billet and fully grind, the mould putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) transition base is put into the Belt-type tools that graphite, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out second step high-pressure synthesis.Pressure is risen to 1GPa, is heated to about 600 DEG C, heat-insulation pressure keeping 180 minutes, then cool release, take out transition base and fully grind, put into acid solution and remove residual raw materials, the powder drying obtained, the mould putting into 10.8mm is prepared into the synthesis base that thickness is 10mm on tabletting machine.
(4) synthesis base spark sintering method is sintered 30 minutes, sintering temperature 680 DEG C, the Na obtaining relative density 97% fills CoSb
3block thermoelectric material.
(5) Na is filled CoSb
3block thermoelectric material is according to requirement of experiment excision forming, use thermal conductivity κ, Seebeck coefficient S and the electricalresistivityρ of laser perturbation thermal conductance instrument (ULVAC-RIKOTC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKOZEM-3) difference test material, and according to formula ZT=S
2t/ ρ κ (wherein T is temperature) calculates its thermoelectric figure of merit ZT.Test the data obtained is drawn and is seen Fig. 5-Fig. 8.
Embodiment 3: high-performance densification Ca fills CoSb
3the preparation method of thermoelectric material
(1) with simple substance Ca (99.99%, powder), Co (99.99%, powder) and Sb (99.99%, powder) for raw material, according to Ca
2co
4sb
12stoichiometric ratio take 8g, the mould putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into the Belt-type tools that graphite, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out the first step high-pressure synthesis.Pressure is risen to 1GPa, is heated to about 800 DEG C, heat-insulation pressure keeping 30 minutes, then cools release, and take out precast billet and fully grind, the mould putting into 10.8mm is prepared into the transition base that thickness is 14mm on tabletting machine.
(3) transition base is put into the Belt-type tools that ink, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out second step high-pressure synthesis.Pressure is risen to 1GPa, is heated to about 600 DEG C, heat-insulation pressure keeping 180 minutes, then cool release, take out transition base and fully grind, put into acid solution and remove residual raw materials, the powder drying obtained, the mould putting into 10.8mm is prepared into the synthesis base that thickness is 10mm on tabletting machine.
(4) synthesis base spark sintering method is sintered 30 minutes, sintering temperature 680 DEG C, the Ca obtaining relative density 96% fills CoSb
3block thermoelectric material.
(5) Ca is filled CoSb
3block thermoelectric material is according to requirement of experiment excision forming, use thermal conductivity κ, Seebeck coefficient S and the electricalresistivityρ of laser perturbation thermal conductance instrument (ULVAC-RIKOTC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKOZEM-3) difference test material, and according to formula ZT=S
2t/ ρ κ (wherein T is temperature) calculates its thermoelectric figure of merit ZT.Test the data obtained is drawn and is seen Fig. 9-Figure 12.
Embodiment 4: high-performance densification Li and Eu dual element fill CoSb
3the preparation method of thermoelectric material
(1) with simple substance Li (99.99%, particle), Eu (99.99%, powder), Co (99.99%, powder) and Sb (99.99%, powder) for raw material, according to LiEuCo
3sb
12stoichiometric ratio take 8g, the mould putting into 10.8mm is prepared into the precast billet that thickness is 16mm on tabletting machine.
(2) precast billet is put into the Belt-type tools that ink, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out the first step high-pressure synthesis.Pressure is risen to 3GPa, is heated to about 800 DEG C, heat-insulation pressure keeping 30 minutes, then cools release, and take out precast billet and fully grind, the mould putting into 10.8mm is prepared into the transition base that thickness is 16mm on tabletting machine.
(3) transition base is put into the Belt-type tools that ink, agalmatolite and boron nitride crucible coordinate composition, in hinge type six-plane piercer, carry out second step high-pressure synthesis.Pressure is risen to 4GPa, is heated to about 600 DEG C, heat-insulation pressure keeping 180 minutes, then release cooling, takes out transition base and fully grinds, put into acid solution and remove residual raw materials, the powder drying obtained, the mould putting into 10.8mm is prepared into the synthesis base that thickness is 10mm on tabletting machine.
(4) synthesis base spark sintering method is sintered 30 minutes, sintering temperature 680 DEG C, the CoSb that Li and the Eu dual element obtaining relative density 98% is filled
3block thermoelectric material.
(5) CoSb of Li and Eu dual element filling
3block thermoelectric material is according to requirement of experiment excision forming, use thermal conductivity κ, Seebeck coefficient S and the electricalresistivityρ of laser perturbation thermal conductance instrument (ULVAC-RIKOTC-7000 and TC-9000) and Seebeck coefficient and resistance test system (ULVAC-RIKOZEM-3) difference test material, and according to formula ZT=S
2t/ ρ κ (wherein T is temperature) calculates its thermoelectric figure of merit ZT.Test the data obtained is drawn and is seen Figure 13-Figure 16.
Claims (10)
1. a high-pressure synthesis preparation method for 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 filling skutterudite thermoelectric material fitted to stoicheiometry feeding and mix, put into mould and be cold-pressed into precast billet, wherein said filling skutterudite thermoelectric material is selected from the binary alloy of lower group: CoP
3, CoAs
3, CoSb
3, RhP
3, RhAs
3, RhSb
3, IrP
3, IrAs
3, IrSb
3; Or be selected from the ternary alloy of lower group: 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 one or more in following element: 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;
(2) the first step high-pressure synthesis: precast billet is put into high-pressure synthesis mould, merges and initial reaction 10-120 minute under the condition of 1-6GPa, 700-900 DEG C, after release cooling, mould is evenly put in products therefrom grinding and is cold-pressed into transition base;
(3) second step high-pressure synthesis: transition base is put into high-pressure synthesis mould, 30-600 minute is reacted under the condition of 1-5GPa, 550-650 DEG C, by even for the filled skutterudite ground material synthesized, pickling removing residual raw materials, drying after cooling release, put into mould and be cold-pressed into synthesis base;
(4) sinter: sinter synthesis base into final block thermoelectric material.
2. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, wherein the reaction times of the first step high-pressure synthesis is 20-60 minute.
3. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, wherein the reaction times of second step high-pressure synthesis is 60-200 minute.
4. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, the grinding wherein in the first step high-pressure synthesis and second step high-pressure synthesis is carried out all under inert gas atmosphere.
5. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, the purity >95% of wherein said element material.
6. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 5, the purity >99% of wherein said element material.
7. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 5, the purity >99.9% of wherein said element material.
8. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, wherein said sintering step utilizes high-pressure sinter or spark sintering technology to carry out.
9. the high-pressure synthesis preparation method of high-performance densification filling skutterudite thermoelectric material as claimed in claim 1, also comprises annealing steps after sintering.
10. the high-performance densification filling skutterudite thermoelectric material that the method according to any one of claim 1-9 obtains, its nondimensional thermoelectric figure of merit ZT>1.
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| CN103924109B (en) * | 2013-11-15 | 2016-02-10 | 武汉理工大学 | The supper-fast preparation high-performance CoSb of a kind of Self-propagating Sintering Synthetic 3the method of base thermoelectricity material |
| CN104332555A (en) * | 2014-09-15 | 2015-02-04 | 燕山大学 | Skutterudite thermoelectric material filled up with iodine, 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 |
| 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 |
| CN106784280A (en) * | 2016-12-22 | 2017-05-31 | 长春理工大学 | A kind of lower thermal conductivity, high zt thermoelectric material |
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| EP0797260A2 (en) * | 1996-03-19 | 1997-09-24 | Ngk Insulators, Ltd. | High temperature thermoelectric material and its production method |
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
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| JPH1140862A (en) * | 1997-07-22 | 1999-02-12 | Yamaguchi Pref Gov Sangyo Gijutsu Kaihatsu Kiko | Manufacture of cobalt antomonide thermoelectric material |
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| EP0797260A2 (en) * | 1996-03-19 | 1997-09-24 | Ngk Insulators, Ltd. | High temperature thermoelectric material and its production method |
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
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| Jianjun Zhang, et al..Thermoelectric properties of n-type CoSb3 fabricated with high pressure sintering.《Journal of Alloys and Compounds》.2010,第503卷第490-493页. * |
| L.Zhang,et al..Impact of high pressure torsion on the microstructure and physical properties of Pr0.67Fe3CoSb12, Pr0.71Fe3.5Ni0.5Sb12 and Ba0.06Co4Sb12.《Journal of Alloys and Compounds》.2010,第494卷第78-83. * |
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