CN102956808B - 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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CN102956808B
CN102956808B CN201210423399.5A CN201210423399A CN102956808B CN 102956808 B CN102956808 B CN 102956808B CN 201210423399 A CN201210423399 A CN 201210423399A CN 102956808 B CN102956808 B CN 102956808B
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thermoelectric element
temperature
high temperature
based compound
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CN102956808A (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 directly heat energy and electric energy mutually transformed, heat energy is converted into electric energy by the Seebeck effect of its utilization itself, except being applied in space industry, generate electricity at waste heat, vehicle exhaust, the fields such as underground heat also have very large potentiality, and in the modern society of energy growing tension, the developed countries and regions that is prepared in of thermoelectric device has obtained enough attention.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.
The thermoelectric device of current investigation and application is single homogeneous thermoelectric material composition, because the thermoelectric material of single homogeneous only obtains maximum in the interval ZT value of limited optimum temperature, after temperature departs from a little, ZT value sharply declines, cause conversion efficiency of thermoelectric lower, hinder development and the application of thermoelectric material greatly.Therefore under the large temperature difference, only have and select the thermoelectric material with different optimum working temperature along temperature gradient direction, make it to connect into multistage thermoelectric element and form gradient-structure ability effective expansion working temperature interval; Every section of material can also be made to be operated in optimum temperature range simultaneously, obtain best thermoelectric figure of merit, effectively improve thermoelectrical efficiency.Bismuth telluride-base thermoelectric material is one of thermoelectric material that low-temperature region ZT value is higher, and current research work also proves CoSb 3base and Zn-Sb based compound are most promising middle high temperature thermoelectric electricity generation material, but to connect due to interface and the various electric heating that exist transport, the difficulties such as flooding mechanism, connection at present about high-temperature thermoelectric material and low-temperature thermoelectric material builds wide temperature range multistage thermoelectric element, particularly relates to CoSb 3base and Zn-Sb based compound are reported considerably less as the research of high temperature section thermoelectric material.The direct sinterings such as the T. Caillat in U.S.'s jet power laboratory (Jet Propulsion Laboratory) have prepared Bi 2te 3/ CoSb 3thermoelectricity section (Energ Convers Manage, 44,2003,1755-1772), due to the without hindrance barrier in interface, inevitably can there is atoms permeating at interface zone when device runs in this direct connected mode, have impact on the doping content of two kinds of thermoelectric materials, reduce thermoelectricity transfer ratio, directly connect due to Bi meanwhile 2te 3and CoSb 3thermal expansion coefficient difference is excessive, and thermal stress that what interface zone was potential also exist is excessive thus cause the problem of cracking.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) has carried out gradient connection (J Electro Mater, 41,2012,1376-1382), the connection of high/low temperature section thermoelectric material have employed the BT/FS composite material of different proportion mixing, this gradient connection causes interface join domain excessive, reduces ZT value to a certain extent, unfavorable to the design of thermoelectric element.
For solving high temperature section CoSb better 3base or type Zn-Sb base thermoelectricity material and low-temperature zone Bi 2te 3the connectivity problem of base thermoelectricity material, build wide temperature range multistage thermoelectric element, the present invention designs and adopts articulamentum to be connected with low-temperature zone thermoelectric material high temperature section, articulamentum is with diffusion impervious layer effect simultaneously, and articulamentum thickness is little, bond strength is high, and the lasting experimental result of heat shows that interface cohesion is good.
summary of the invention:
In order to solve the problems of the technologies described above, the invention provides wide temperature range thermoelectric element, providing its preparation method simultaneously.High temperature section is connected with low-temperature zone thermoelectric material by selecting suitable articulamentum by the present invention, and bond strength is high and can reduce the impact that transports electric heating to greatest extent.
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's design is the one in Cu, Nb or Mo layer.
Described CoSb 3based compound, with CoSb 3for matrix, and to fill wherein or Li doped, one or more elements in Ir, Pr, Sm, Er, Yb, Y or Pd are prepared from.
Described Zn-Sb based compound is with Zn and Sb for host element, and one or more elements in Yb, Ca, Cd, Mg, Ga, In or Eu that adulterate.
Described Bi-Te based compound is using Bi and Te as principal component, doping Te I 4, SbI 3or SbBr 3in one or more to be prepared from.
Preparation technology of the present invention is simple and convenient, and hot lasting effects is better, is conducive to the long service of wide temperature range multistage thermoelectric element.Adopt the method for discharge plasma sintering high temperature section and low-temperature zone thermoelectric material to be carried out being connected and prepare, concrete step is as follows:
1) get high temperature section block and low-temperature zone block, carry out sandblasting pretreatment on its surface, make its surface have surface roughness;
2) by high temperature section block and low-temperature zone block thermoelectric material in alcohol ultrasonic 3 ~ 5 minutes, connecting surface cleaning is carried out to it, removes impurity particle;
3) articulamentum material can adopt connection paillon foil, first adopts fine sandpaper polishing 2 ~ 3 minutes, then alcohol ultrasonic cleaning 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 platinum at agate and grind 30 ~ 50 minutes with alcohol, dry rear taking-up;
4) graphite jig is got, put into low-temperature zone block thermoelectric material, articulamentum and high temperature section thermoelectric material successively, 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 DEG C/min, and sintering temperature is 580 ~ 600 DEG C, then 10 ~ 30min is incubated, deposition; Described high temperature section block is identical with low-temperature zone block conduction type, is all P type or N-type;
5), after deposition, continue to keep vacuum state, when temperature is cooled to 100 DEG C, put vacuum, take out the thermoelectric element sintered in graphite jig, obtain wide temperature range thermoelectric element.
The present invention utilizes discharge plasma sintering process by middle foil articulamentum by high-temperature thermoelectric material (CoSb 3base or Zn-Sb yl) and low-temperature thermoelectric material (Bi 2te 3base) connect, construct wide temperature range multistage thermoelectric element, multistage component interface bond strength is high, interface zone is little, farthest reduce the impact that interface transports electric heating, solve the shortcoming that single thermoelectric element high zt temperature range is little, and heat lasting experiment rear interface combines good.
The invention has the beneficial effects as follows:
(1) wide temperature range multistage thermoelectric element solves the less drawback of single hop thermoelectric element temperature range;
(2) the multi-segment structure interface bond strength adopting intermediate connecting layer to connect is greater than 10MPa;
(3) multistage thermoelectric element sample is 500 ounder C condition, the lasting experiment of heat is after 30 days, and interface zone combines good, without obvious diffusion phenomena.
accompanying drawing illustrates:
Fig. 1: adopt the Bi that Mo layer connects 2te 3/ CoSb 3the SEM scanned photograph at interface.
Fig. 2: adopt the Bi that Nb layer connects 2te 3/ Zn 4sb 3the SEM scanned photograph at interface.
Fig. 3: adopt the Bi that Cu layer connects 0.5sb 1.5te 3/ Zn 4sb 3the SEM scanned photograph at interface.
embodiment:
Below by way of instantiation, the present invention is described.
embodiment 1
Connect intermediate layer and adopt Mo layer (powder) composition, high temperature section thermoelectric material adopts CoSb 3, low-temperature zone thermoelectric material adopts Bi 2te 3.First by block CoSb 3and Bi 2te 3blasting treatment is carried out on surface, dries up in alcohol after ultrasonic 3 min, Mo powder agate grind grind 30min in platinum after dry taking-up; Then by Bi 2te 3put into graphite jig, Mo powder is layered on Bi uniformly 2te 3on block, then by block CoSb 3put into graphite jig, pressure head starts to carry out discharge plasma sintering after compressing.Wherein vacuum degree 5Pa, sintering pressure is 50 MPa, and heating rate is 120 DEG C/min, and sintering temperature is 580 DEG C, is then incubated 10min; After treat that mold temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete 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 cohesion good (Fig. 1), interface bond strength is 11.6Mpa; 500 ounder C condition, the lasting experiment of heat is after 20 days, Bi 2te 3/ CoSb 3thermoelectric element interface zone is without obvious diffusion phenomena.
embodiment 2
Connect intermediate layer and adopt Nb paper tinsel, high temperature section thermoelectric material adopts Zn 4sb 3, low-temperature zone thermoelectric material adopts Bi 2te 3.First by block CoSb 3and Bi 2te 3blasting treatment is carried out on surface, dries up in alcohol after ultrasonic 3 min, takes out and dry up after the polishing of Nb paper tinsel fine sandpaper in alcohol after ultrasonic 2min; Then by Bi 2te 3, Nb paper tinsel and Zn 4sb 3put into graphite jig successively, pressure head starts to carry out discharge plasma sintering after compressing.Wherein vacuum degree 15Pa, sintering pressure is 60 MPa, and heating rate is 180 DEG C/min, and sintering temperature is 600 DEG C, is then incubated 30min; After treat that mold temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete 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 cohesion good (Fig. 2), interface bond strength is 12.8Mpa; 500 ounder C condition, the lasting experiment of heat is after 20 days, Bi 2te 3/ Zn 4sb 3thermoelectric element interface zone is without obvious diffusion phenomena.
embodiment 3
Connect intermediate layer and adopt Cu paper tinsel, high temperature section thermoelectric material adopts Zn 4sb 3, low-temperature zone thermoelectric material adopts Bi 0.5sb 1.5te 3.First by block Zn 4sb 3and Bi 0.5sb 1.5te 3blasting treatment is carried out on surface, dries up in alcohol after ultrasonic 5min, takes out and dry up after the polishing of Nb paper tinsel fine sandpaper in alcohol after ultrasonic 3min; Then by Bi 0.5sb 1.5te 3, Cu paper tinsel and Zn 4sb 3put into graphite jig successively, pressure head starts to carry out discharge plasma sintering after compressing.Wherein vacuum degree 10Pa, sintering pressure is 55 MPa, and heating rate is 150 DEG C/min, and sintering temperature is 590 DEG C, is then incubated 20min; After treat that mold temperature is cooled to 100 DEG C, open vacuum chamber take out sample, complete 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 cohesion good (Fig. 3), interface bond strength is 13.2Mpa; 500 ounder C, the lasting experiment of heat is after 20 days, Bi 0.5sb 1.5te 3/ Zn 4sb 3thermoelectric element interface zone is without obvious diffusion phenomena.
embodiment 4
Connect intermediate layer and adopt Cu layer (powder), high temperature section thermoelectric material adopts Y 0.1co 4sb 12, 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 cohesion is good, and interface bond strength is 13.4Mpa; 500 oc heat is lasting tests after 20 days, Bi 2te 3/ Y 0.1co 4sb 12thermoelectric element interface zone is without obvious diffusion phenomena.
embodiment 5
Connect intermediate layer and adopt Nb layer (powder), high temperature section thermoelectric material adopts Ir 0.08co 4sb 12, 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 cohesion is 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 12thermoelectric element interface zone is without obvious diffusion phenomena.

Claims (3)

1. a wide temperature range thermoelectric element, comprises high temperature section and low-temperature zone, it is characterized in that, connect with articulamentum between described high temperature section and low-temperature zone, the material of described articulamentum is the one in Cu, Nb or 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 Bi-Te based compound:
Bonding strength between described articulamentum and high temperature section or low-temperature zone is greater than 10MPa:
Described Bi-Te based compound is using Bi and Te as principal component, doping Te I 4, SbI 3or SbBr 3in one or more to be prepared from;
Described CoSb 3based compound, with CoSb 3for matrix, and to fill wherein or Li doped, one or more elements in Ir, Pr, Sm, Er, Yb, Y or Pd are prepared from;
Described Zn-Sb based compound is with Zn and Sb for host element, and one or more elements in Yb, Ca, Cd, Mg, Ga, In or Eu that adulterate.
2. a preparation method for wide temperature range thermoelectric element according to claim 1, comprises the following steps:
1) material getting preparation high temperature section and low-temperature zone carries out sandblasting pretreatment, makes its surface have surface roughness;
2) by high temperature section and low-temperature zone material in alcohol ultrasonic 3 ~ 5 minutes, connecting surface cleaning is carried out to it, removes impurity particle;
3) get articulamentum material, cleaning, dries;
4) graphite jig is got, put into low-temperature zone material, articulamentum material and high temperature section material successively, 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 DEG C/min, sintering temperature is 580 ~ 600 DEG C, is then 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), after deposition, continue to keep vacuum state, when temperature is cooled to 100 DEG C, put vacuum, take out and obtain wide temperature range thermoelectric element.
3. preparation method according to claim 2, it is characterized in that, described articulamentum material is a kind of paillon foil prepared in Cu, Nb or Mo, and described cleaning step is first adopt fine sandpaper polishing 2 ~ 3 minutes, then alcohol ultrasonic cleaning 3 ~ 5 minutes, removes surface impurity particle and spot.
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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CN101114692A (en) * 2007-08-10 2008-01-30 中国科学院上海硅酸盐研究所 Method for manufacturing cobalt stibium antimonide based thermoelectric device
CN101794858A (en) * 2009-12-25 2010-08-04 北京工业大学 P-type (Bi0.25Sb0.75)2Te3/CeyFe4Sb12(y=0.8-1.2)-based bulk gradient thermoelectric material and preparation method thereof

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CN101114692A (en) * 2007-08-10 2008-01-30 中国科学院上海硅酸盐研究所 Method for manufacturing cobalt stibium antimonide based thermoelectric device
CN101794858A (en) * 2009-12-25 2010-08-04 北京工业大学 P-type (Bi0.25Sb0.75)2Te3/CeyFe4Sb12(y=0.8-1.2)-based bulk gradient thermoelectric material and preparation method thereof

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Bi2Te3/CoSb3宽温域热电材料的制备、界面结构与和力学性能;刘刚;《中国优秀硕士学位论文全文数据库工程科技I辑》;20121015(第10期);第48页第4.2.1节至49页4.2.2节、附图4-2至4-6 *

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