CN102956808A - Thermoelectric element with wide temperature region and preparation method thereof - Google Patents

Thermoelectric element with wide temperature region and preparation method thereof Download PDF

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CN102956808A
CN102956808A CN2012104233995A CN201210423399A CN102956808A CN 102956808 A CN102956808 A CN 102956808A CN 2012104233995 A CN2012104233995 A CN 2012104233995A CN 201210423399 A CN201210423399 A CN 201210423399A CN 102956808 A CN102956808 A CN 102956808A
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thermoelectric element
low
articulamentum
high temperature
based compound
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CN102956808B (en
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赵德刚
左敏
耿浩然
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University of Jinan
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University of Jinan
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Abstract

The invention relates to a thermoelectric element with a wide temperature region. The thermoelectric element comprises a high-temperature section and a low-temperature section which are connected by virtue of a connecting layer, wherein the connecting layer is made of one of Cu, Nb and Mo; the high-temperature section is made of CoSb3-based compound or a Zn-Sb-based compound; and the low-temperature section is made of Bi-Te-based compound. Meanwhile, the invention further provides a preparation method of the thermoelectric element with the wide temperature region. According to the method, the high-temperature section, the connecting layer and the low-temperature section are connected by virtue of a spark plasma sintering technology. The thermoelectric element with the wide temperature region, provided by the invention, is high in bonding strength and large in temperature region, and has no obvious interface diffusion phenomenon.

Description

A kind of wide temperature range thermoelectric element and preparation method thereof
Technical field
The present invention relates to a kind of wide temperature range thermoelectric element, belong to thermoelectric material and devices field, the present invention also relates to the preparation method of this wide temperature range thermoelectric element simultaneously.
Background technology
Thermoelectric material is a kind of functional material that directly heat energy and electric energy is transformed mutually, the Seebeck effect of its utilization itself is converted into electric energy with heat energy, except being applied in space industry, in used heat cogeneration, vehicle exhaust, the fields such as underground heat also have very large potentiality, and in the modern society of energy growing tension, the preparation of thermoelectric device has obtained enough attention in developed country and area.The conversion efficiency of thermoelectric device depends on the thermoelectric figure of merit ZT of material, wherein ZT=S greatly 2T/ ρ κ, S are Seebeck coefficient, and ρ is resistivity, and κ is thermal conductivity, and T is absolute temperature.
At present research and the thermoelectric device of using are single homogeneous thermoelectric material and form, because the thermoelectric material of single homogeneous is only obtained maximum in the interval ZT value of limited optimum temperature, after temperature departs from a little, the ZT value sharply descends, cause conversion efficiency of thermoelectric lower, hindered greatly development and the application of thermoelectric material.Therefore under the large temperature difference, only have along the temperature gradient direction and select the thermoelectric material with different optimum working temperatures, effectively the expansion working temperature is interval to make it to connect into multistage thermoelectric element formation gradient-structure; Can also obtain best thermoelectric figure of merit so that every section material is operated in the optimum temperature range simultaneously, effectively improve thermoelectrical efficiency.Bismuth telluride-base thermoelectric material is one of higher thermoelectric material of low-temperature region ZT value, and present research work also proves CoSb 3Base and Zn-Sb based compound are most promising middle high temperature thermoelectric power generation materials, yet because the difficulties such as the interface connects and the various electric heating of existence transport, flooding mechanism, at present be connected connection with low-temperature thermoelectric material about the high temperature thermoelectric material and make up wide temperature range multistage thermoelectric element, relate in particular to CoSb 3Base and Zn-Sb based compound are considerably less as the research report of high temperature section thermoelectric material.The direct sinterings such as T. Caillat in U.S. jet power laboratory (Jet Propulsion Laboratory) have prepared Bi 2Te 3/ CoSb 3Thermoelectric section (Energ Convers Manage, 44,2003,1755-1772), this direct connected mode is because inevitably can there be the atom diffusion in the unobstructed layer in interface at interface zone when device moves, affected the doping content of two kinds of thermoelectric materials, reduced thermoelectric transfer ratio, simultaneously, directly connected because Bi 2Te 3And CoSb 3Thermal expansion coefficient difference is excessive, thus the potential excessive problem that causes cracking of thermal stress that exists of interface zone.Professor Zhang Qingjie of Wuhan University of Technology is to Bi 2Te 2.7Se 0.3/ Ba 0.4In 0.4Co 4Sb 12(being called for short BT/FS) carried out gradient connection (J Electro Mater, 41,2012,1376-1382), the BT/FS composite material that the connection of high low-temperature zone thermoelectric material has adopted different proportion to mix, this gradient connection causes the interface join domain excessive, has reduced to a certain extent the ZT value, and is unfavorable to the design of thermoelectric element.
For solving better high temperature section CoSb 3Base or Zn-Sb base thermoelectricity material and low-temperature zone Bi 2Te 3The connectivity problem of base thermoelectricity material, make up wide temperature range multistage thermoelectric element, the present invention designs and adopts articulamentum that high temperature section is connected with the low-temperature zone thermoelectric material, articulamentum is with the diffusion impervious layer effect simultaneously, and articulamentum thickness is little, bond strength is high, and the lasting experimental result of heat shows that the interface is in conjunction with good.
Summary of the invention:
In order to solve the problems of the technologies described above, the invention provides wide temperature range thermoelectric element, its preparation method is provided simultaneously.The present invention is by selecting suitable articulamentum that high temperature section is connected with the low-temperature zone thermoelectric material, and bond strength is high and can reduce to greatest extent impact that electric heating is transported.
The present invention is applicable to CoSb 3Based compound or Zn-Sb based compound thermoelectric material are as high temperature section and low-temperature zone Bi 2Te 3The connection of base thermoelectricity material, the material of the intermediate connecting layer of the present invention design are a kind of in Cu, Nb or the Mo layer.
Described CoSb 3Based compound is with CoSb 3Be matrix, and one or more elements among therein filling or Li doped, Ir, Pr, Sm, Er, Yb, Y or the Pd are prepared from.
Described Zn-Sb based compound is take Zn and Sb as host element, and one or more elements among doping Yb, Ca, Cd, Mg, Ga, In or the Eu.
Described Bi-Te based compound, be with Bi and Te as principal component, doping Te I 4, SbI 3Or SbBr 3In one or more be prepared from.
Preparation technology of the present invention is simple and convenient, and the lasting effect of heat is better, is conducive to the long service of wide temperature range multistage thermoelectric element.Adopt the method for discharge plasma sintering that high temperature section is connected preparation with the low-temperature zone thermoelectric material, concrete step is as follows:
1) gets high temperature section block and low-temperature zone block, carry out sandblasting pretreatment on its surface, make its surface have surface roughness;
2) with high temperature section block and low-temperature zone block thermoelectric material in alcohol ultrasonic 3～5 minutes, it is carried out connecting surface clean, remove impurity particle;
3) the articulamentum material can adopt the connection paillon foil, adopts first fine sandpaper polishing 2～3 minutes, and then the alcohol ultrasonic cleaning is 3～5 minutes, removes surface impurity particle and spot; Described connection paillon foil is Cu, Nb and Mo;
Articulamentum also can adopt powder, powder need be ground in the platinum at agate and grind 30～50 minutes with alcohol, dries rear taking-up;
4) get graphite jig, put into successively low-temperature zone block thermoelectric material, articulamentum and high temperature section thermoelectric material, compress pressure head, after carry out discharge plasma sintering, wherein, vacuum degree 5～15Pa, sintering pressure is 50～60 MPa, and heating rate is 120～180 ℃/min, and sintering temperature is 580～600 ℃, then be incubated 10～30min, deposition; Described high temperature section block is identical with low-temperature zone block conduction type, is all P type or N-type;
5) deposition complete after, continue to keep vacuum state, when treating that temperature is cooled to 100 ℃, put vacuum, take out the thermoelectric element that sinters in the graphite jig, get wide temperature range thermoelectric element.
The present invention utilizes discharge plasma sintering process to pass through middle paillon foil articulamentum with high temperature thermoelectric material (CoSb 3Base or Zn-Sb yl) and low-temperature thermoelectric material (Bi 2Te 3Base) connect, made up wide temperature range multistage thermoelectric element, multistage component interface bond strength is high, interface zone is little, farthest reduced the interface to the impact that electric heating transports, solved the little shortcoming of the high ZT value of single thermoelectric element temperature range, and the lasting experiment of heat rear interface is in conjunction with good.
The invention has the beneficial effects as follows:
(1) wide temperature range multistage thermoelectric element has solved the less drawback of single hop thermoelectric element temperature range;
(2) adopt the multi-segment structure interface bond strength of intermediate connecting layer connection greater than 10MPa;
(3) multistage thermoelectric element sample is 500 oLastingly experiment of heat is after 30 days under the C condition, and interface zone is in conjunction with good, without obvious diffusion phenomena.
Description of drawings:
Fig. 1: the Bi that adopts the Mo layer to connect 2Te 3/ CoSb 3The SEM scanned photograph at interface.
Fig. 2: the Bi that adopts the Nb layer to connect 2Te 3/ Zn 4Sb 3The SEM scanned photograph at interface.
Fig. 3: the Bi that adopts the Cu layer to connect 0.5Sb 1.5Te 3/ Zn 4Sb 3The SEM scanned photograph at interface.
Embodiment:
Below by instantiation the present invention is described.
Embodiment 1
Connect the intermediate layer and adopt Mo layer (powder) composition, the high temperature section thermoelectric material adopts CoSb 3, the low-temperature zone thermoelectric material adopts Bi 2Te 3At first with block CoSb 3And Bi 2Te 3Blasting treatment is carried out on the surface, dries up behind ultrasonic 3 min in alcohol, and the Mo powder grinds in the platinum at agate and dries taking-up behind the grinding 30min; Then with Bi 2Te 3Put into graphite jig, the Mo powder is layered on Bi uniformly 2Te 3On the block, again with block CoSb 3Put into graphite jig, pressure head begins to carry out discharge plasma sintering after compressing.Vacuum degree 5Pa wherein, sintering pressure is 50 MPa, and heating rate is 120 ℃/min, and sintering temperature is 580 ℃, then is incubated 10min; Treat after complete that mold temperature is cooled to 100 ℃, open vacuum chamber and take out sample, finish multistage Bi 2Te 3/ CoSb 3The preparation process of thermoelectric element.
The multistage Bi of this example gained 2Te 3/ CoSb 3Thermoelectric element, its interface is in conjunction with good (Fig. 1), and interface bond strength is 11.6Mpa; 500 oHeat is lasting under the C condition tests after 20 days Bi 2Te 3/ CoSb 3The thermoelectric element interface zone is without obvious diffusion phenomena.
Embodiment 2
Connect the intermediate layer and adopt the Nb paper tinsel, the high temperature section thermoelectric material adopts Zn 4Sb 3, the low-temperature zone thermoelectric material adopts Bi 2Te 3At first with block CoSb 3And Bi 2Te 3Blasting treatment is carried out on the surface, dries up behind ultrasonic 3 min in alcohol, and the Nb paper tinsel dries up with rear the taking-up behind the ultrasonic 2min in alcohol of fine sandpaper polishing; Then with Bi 2Te 3, Nb paper tinsel and Zn 4Sb 3Put into successively graphite jig, pressure head begins to carry out discharge plasma sintering after compressing.Vacuum degree 15Pa wherein, sintering pressure is 60 MPa, and heating rate is 180 ℃/min, and sintering temperature is 600 ℃, then is incubated 30min; Treat after complete that mold temperature is cooled to 100 ℃, open vacuum chamber and take out sample, finish multistage Bi 2Te 3/ Zn 4Sb 3The preparation process of thermoelectric element.
The multistage Bi of this example gained 2Te 3/ Zn 4Sb 3Thermoelectric element, its interface is in conjunction with good (Fig. 2), and interface bond strength is 12.8Mpa; 500 oHeat is lasting under the C condition tests after 20 days Bi 2Te 3/ Zn 4Sb 3The thermoelectric element interface zone is without obvious diffusion phenomena.
Embodiment 3
Connect the intermediate layer and adopt the Cu paper tinsel, the high temperature section thermoelectric material adopts Zn 4Sb 3, the low-temperature zone thermoelectric material adopts Bi 0.5Sb 1.5Te 3At first with block Zn 4Sb 3And Bi 0.5Sb 1.5Te 3Blasting treatment is carried out on the surface, dries up behind the ultrasonic 5min in alcohol, and the Nb paper tinsel dries up with rear the taking-up behind the ultrasonic 3min in alcohol of fine sandpaper polishing; Then with Bi 0.5Sb 1.5Te 3, Cu paper tinsel and Zn 4Sb 3Put into successively graphite jig, pressure head begins to carry out discharge plasma sintering after compressing.Vacuum degree 10Pa wherein, sintering pressure is 55 MPa, and heating rate is 150 ℃/min, and sintering temperature is 590 ℃, then is incubated 20min; Treat after complete that mold temperature is cooled to 100 ℃, open vacuum chamber and take out sample, finish multistage Bi 0.5Sb 1.5Te 3/ Zn 4Sb 3The preparation process of thermoelectric element.
The multistage Bi of this example gained 0.5Sb 1.5Te 3/ Zn 4Sb 3Thermoelectric element, its interface is in conjunction with good (Fig. 3), and interface bond strength is 13.2Mpa; 500 oHeat is lasting under the C tests after 20 days Bi 0.5Sb 1.5Te 3/ Zn 4Sb 3The thermoelectric element interface zone is without obvious diffusion phenomena.
Embodiment 4
Connect the intermediate layer and adopt Cu layer (powder), the high temperature section thermoelectric material adopts Y 0.1Co 4Sb 12, the low-temperature zone thermoelectric material adopts Bi 2Te 3
The preparation technology of multistage thermoelectric element is with embodiment 1.
The multistage Bi of this example gained 2Te 3/ Y 0.1Co 4Sb 12Thermoelectric element, its interface is in conjunction with good, and interface bond strength is 13.4Mpa; 500 oC heat is lasting tests after 20 days Bi 2Te 3/ Y 0.1Co 4Sb 12The thermoelectric element interface zone is without obvious diffusion phenomena.
Embodiment 5
Connect the intermediate layer and adopt Nb layer (powder), the high temperature section thermoelectric material adopts Ir 0.08Co 4Sb 12, the low-temperature zone thermoelectric material adopts Bi 0.5Sb 1.5Te 3
The preparation technology of multistage thermoelectric element is with embodiment 1.
The multistage Bi of this example gained 0.5Sb 1.5Te 3/ Ir 0.08Co 4Sb 12Thermoelectric element, its interface is in conjunction with good, and interface bond strength is 12.9Mpa; 500 oC heat is lasting tests after 20 days Bi 0.5Sb 1.5Te 3/ Ir 0.08Co 4Sb 12The thermoelectric element interface zone is without obvious diffusion phenomena.

Claims (9)

1. one kind wide temperature range thermoelectric element comprises high temperature section and low-temperature zone, it is characterized in that, connects with articulamentum between described high temperature section and the low-temperature zone, and the material of described articulamentum is a kind of among Cu, Nb or the Mo; The material of described high temperature section is CoSb 3Based compound or Zn-Sb based compound; The material of described low-temperature zone is the Bi-Te based compound.
2. wide temperature range thermoelectric element according to claim 1 is characterized in that, the thickness of described articulamentum is 50～500um.
3. wide temperature range thermoelectric element according to claim 1 and 2 is characterized in that, the bonding strength between described articulamentum and high temperature section or the low-temperature zone is greater than 10MPa.
4. wide temperature range thermoelectric element according to claim 1 is characterized in that, described Bi-Te based compound, be with Bi and Te as principal component, doping Te I 4, SbI 3Or SbBr 3In one or more be prepared from.
5. wide temperature range thermoelectric element according to claim 1 is characterized in that described CoSb 3Based compound is with CoSb 3Be matrix, and one or more elements among therein filling or Li doped, Ir, Pr, Sm, Er, Yb, Y or the Pd are prepared from.
6. wide temperature range thermoelectric element according to claim 1 is characterized in that, described Zn-Sb based compound is take Zn and Sb as host element, and one or more elements among doping Yb, Ca, Cd, Mg, Ga, In or the Eu.
7. the preparation method of each described wide temperature range thermoelectric element among the claim 1-6 may further comprise the steps:
1) material of getting preparation high temperature section and low-temperature zone carries out sandblasting pretreatment, makes its surface have surface roughness;
2) with high temperature section and low-temperature zone material in alcohol ultrasonic 3～5 minutes, it is carried out connecting surface clean, remove impurity particle;
3) get the articulamentum material, clean, dry;
4) get graphite jig, put into successively low-temperature zone material, articulamentum material and high temperature section material, after compressing pressure head, carry out discharge plasma sintering, control vacuum degree is 5～15Pa, and sintering pressure is 50～60 MPa, and heating rate is 120～180 ℃/min, sintering temperature is 580～600 ℃, then is incubated 10～30min deposition; Described high temperature section material is identical with the conduction type of low-temperature zone material, is all P type or N-type;
5) deposition complete after, continue to keep vacuum state, when treating that temperature is cooled to 100 ℃, put vacuum, take out and namely get wide temperature range thermoelectric element.
8. preparation method according to claim 7, it is characterized in that, described articulamentum material is a kind of paillon foil for preparing of Cu, Nb or Mo, and described cleaning step is for adopting first fine sandpaper polishing 2～3 minutes, then the alcohol ultrasonic cleaning is 3～5 minutes, removes surface impurity particle and spot.
9. preparation method according to claim 7, it is characterized in that, described articulamentum material is a kind of powder for preparing among Cu, Nb or the Mo, and described cleaning step grinds 30～50 minutes to 300～500 orders for powder is ground in the platinum at agate with alcohol, dries rear taking-up.
CN201210423399.5A 2012-10-30 2012-10-30 Thermoelectric element with wide temperature region and preparation method thereof Expired - Fee Related CN102956808B (en)

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Publication number Priority date Publication date Assignee Title
CN107681044A (en) * 2017-10-16 2018-02-09 中国科学院上海硅酸盐研究所 A kind of wide temperature range Thermoelectric Generator of multi-segment structure and preparation method
CN107681044B (en) * 2017-10-16 2020-08-14 中国科学院上海硅酸盐研究所 Multi-section structure wide temperature range thermoelectric power generation device and preparation method thereof

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