CN113860873B - Bismuth telluride thermoelectric device and preparation method thereof - Google Patents

Bismuth telluride thermoelectric device and preparation method thereof Download PDF

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CN113860873B
CN113860873B CN202111218230.1A CN202111218230A CN113860873B CN 113860873 B CN113860873 B CN 113860873B CN 202111218230 A CN202111218230 A CN 202111218230A CN 113860873 B CN113860873 B CN 113860873B
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bismuth telluride
powder
barrier layer
layer
telluride thermoelectric
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CN113860873A (en
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纽春萍
何海龙
虞珂
荣命哲
吴翊
田昊洋
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Xian Jiaotong University
State Grid Shanghai Electric Power Co Ltd
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Xian Jiaotong University
State Grid Shanghai Electric Power Co Ltd
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention discloses a preparation method of a bismuth telluride thermoelectric device, which comprises the following steps: selecting a proper amount of Ni powder raw material and C powder raw material, mixing and then ball-milling to obtain Ni-C mixed powder; filling a proper amount of bismuth telluride powder into the grinding tool and prepressing to form a bismuth telluride thermoelectric material layer; drying the Ni-C mixed powder, filling the dried Ni-C mixed powder into a grinding tool, and uniformly accumulating the powder on the bismuth telluride thermoelectric material layer for secondary prepressing to form a Ni-C barrier layer; and performing SPS sintering on the bismuth telluride thermoelectric material layer and the Ni-C barrier layer, and cooling to obtain the bismuth telluride thermoelectric device. According to the method, the C raw material is selected to partially replace the Ni raw material, so that the diffusion and reaction of Ni elements and Te elements at the interfaces of the bismuth telluride hot spot material layer and the barrier layer can be reduced to a certain extent, and the degradation of the bismuth telluride thermoelectric material layer and the interface of the Ni-C barrier layer can be inhibited to a certain extent.

Description

Bismuth telluride thermoelectric device and preparation method thereof
Technical Field
The disclosure belongs to the technical field of energy conversion, and particularly relates to a bismuth telluride thermoelectric device and a preparation method thereof.
Background
The thermoelectric material is a functional material capable of realizing conversion of heat energy and electric energy. The thermoelectric conversion technology is based on the Seebeck effect, and the thermoelectric conversion technology can realize the mutual conversion of heat energy and electric energy by driving the carrier migration to form thermoelectric electromotive force through temperature difference. The thermoelectric power generation device made of thermoelectric material can utilize industrial and commercial waste heat, terrestrial heat and human bodyThe temperature and the like are used as heat sources for thermoelectric conversion, and the device has the advantages of small volume, high stability, long service life, environmental protection, no maintenance and the like. The thermoelectric conversion technology can directly convert electric energy into heat energy, effectively realizes reutilization of waste heat generated in industry and life, and has important significance in improving energy utilization rate, energy structure and environment protection. The key to thermoelectric conversion technology lies in the level of thermoelectric material performance and the level of power generation device technology. As for the material, the thermoelectric material currently applied in the low temperature region mainly comprises Bi 2 Te 3 And Ag 2 Se。Bi 2 Te 3 The thermoelectric material is researched earliest and most mature, is the thermoelectric material which is most applied in the room temperature range at present, and the thermoelectric device prepared on the basis of the bismuth telluride material is also widely applied in the room temperature range. For thermoelectric devices, the design and implementation of the topological structure (geometry, size, connection mode, current-heat flow coupling matching, etc.) and the structure of a heterogeneous interface (electrode-thermoelectric material, electrode-insulating substrate, etc.) of the device are core problems of the device integration technology. In a conventional thermoelectric device, an electrode is directly connected to a thermoelectric material by a solder, and due to differences in connection process and solder, the interfacial resistance between the electrode and the thermoelectric material may differ by orders of magnitude. During service, reaction and diffusion can occur between the solder and the thermoelectric material, so that the contact resistance and the bonding strength of an interface are greatly deteriorated, and finally, the thermoelectric device fails. Therefore, the interface problem is the most critical contributing factor to the failure of thermoelectric devices.
At present, a barrier layer is generally added between an electrode and a thermoelectric material to solve the device failure caused by the interface problem between solder and the thermoelectric material. For P-type bismuth telluride, ni is a barrier layer material applied to a low-temperature bismuth telluride device, however, although Ni can significantly reduce the contact resistance between solder and thermoelectric material at the interface, ni and Te form Ni at the interface x Te y The compounds cause an increase in interfacial contact resistance and thus a reduction in the conversion efficiency of the thermoelectric device, this degradation being particularly pronounced at temperatures above 200 ℃. For bismuth N-telluride, co-P layerIs a better barrier layer material, and the existing research shows that the contact resistance at the interface of Co-P and N-type bismuth telluride can be from 60 mu omega cm after aging for 15 days under the air atmosphere at the temperature of 150 DEG C 2 Rise to 80 mu omega cm 2 The contact resistance thereof is to be further reduced. Therefore, it is necessary to select a high-performance barrier layer more suitable for the bismuth telluride thermoelectric device to ensure the service long-term performance and service stability of the device.
Disclosure of Invention
Aiming at the defects in the prior art, the disclosed bismuth telluride thermoelectric device and the preparation method thereof are characterized in that a C raw material is selected to partially replace a Ni raw material, so that the diffusion and reaction of Ni elements and Te elements in a reaction layer at the interface of a bismuth telluride hot spot material layer and a barrier layer can be reduced to a certain extent.
In order to achieve the above purpose, the present disclosure provides the following technical solutions:
a preparation method of a bismuth telluride thermoelectric device comprises the following steps:
s100: selecting a proper amount of Ni powder raw material and C powder raw material, mixing and then ball-milling to obtain Ni-C mixed powder;
s200: filling a proper amount of bismuth telluride powder into the grinding tool and prepressing to form a bismuth telluride thermoelectric material layer;
s300: drying the Ni-C mixed powder, filling the dried Ni-C mixed powder into a grinding tool, and uniformly accumulating the dried Ni-C mixed powder on the bismuth telluride thermoelectric material layer for secondary prepressing to form a Ni-C barrier layer;
s400: and sintering the bismuth telluride thermoelectric material layer and the Ni-C barrier layer to obtain the bismuth telluride thermoelectric device.
Preferably, in step S100, the mass ratio of the Ni powder material to the C powder material is 4: 1.
Preferably, in step S100, the ball milling is intermittent ball milling, the ball milling is stopped for 0.5h after 2h, and the ball milling time is 8h.
Preferably, in the step S200 and the step S300, the bismuth telluride powder is pre-pressed under the pressure of 20MPa, and the Ni-C mixed powder is pre-pressed for the second time.
Preferably, in step S200, the Ni-C mixed powder is dried for 18 hours in an environment with the vacuum degree of less than or equal to 0.1Pa and the temperature of 80 ℃.
Preferably, in step S300, after the Ni — C barrier layer is formed, it is also required to perform thinning treatment.
Preferably, the thickness of the Ni-C barrier layer after thinning treatment is 0.2mm to 0.5mm.
Preferably, in step S400, a gradient temperature rise is adopted during the sintering process.
Preferably, in step S400, pressure is maintained during the whole sintering process, wherein the pressure is 45MPa.
The present disclosure also provides a bismuth telluride thermoelectric device, including: the thermoelectric material layer comprises a bismuth telluride thermoelectric material layer and a barrier layer, wherein the barrier layer comprises 80wt% of Ni powder and 20wt% of C powder.
Compared with the prior art, the beneficial effect that this disclosure brought does: by selecting the C raw material part to replace the Ni raw material, the diffusion and reaction of Ni and Te elements at the interfaces of the bismuth telluride hot spot material layer and the barrier layer can be reduced to a certain extent, the good interface resistance and bonding strength of Ni as the barrier layer can be retained, the service performance of the device under the low-temperature condition can be improved, and the deterioration of the bismuth telluride thermoelectric material layer and the pure Ni barrier layer can be inhibited to a certain extent.
Drawings
Fig. 1 is a flow chart of a method for manufacturing a bismuth telluride thermoelectric device according to an embodiment of the present disclosure;
FIG. 2 is an SEM image of an interface of a Ni-C barrier layer and a P-type bismuth telluride aged at 200 ℃ for 100 hours in an air atmosphere according to another embodiment of the disclosure;
FIG. 3 is a contact resistance of an unaged Ni-C barrier layer with bismuth P-telluride provided by another embodiment of the present disclosure;
FIG. 4 is a graph of the contact resistance of a Ni-C barrier layer and a P-type bismuth telluride layer aged at 200 ℃ for 100 hours in an air atmosphere according to another embodiment of the disclosure;
FIG. 5 is an SEM image of an interface of a Ni-C barrier layer and bismuth N-telluride aged at 150 ℃ in an air atmosphere for 15 days according to another embodiment of the disclosure;
FIG. 6 is a contact resistance of an unaged Ni-C barrier layer and bismuth N-telluride provided by another embodiment of the present disclosure;
fig. 7 is a graph of the contact resistance of a Ni-C barrier layer and bismuth N-telluride aged at 150 ℃ in an air atmosphere for 15 days according to another embodiment of the disclosure.
Detailed Description
Specific embodiments of the present disclosure will be described in detail below with reference to fig. 1 to 7. While specific embodiments of the disclosure are shown in the drawings, it should be understood that the disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
It should be noted that certain terms are used throughout the description and following claims to refer to particular components. As one skilled in the art will appreciate, various names may be used to refer to a component. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the present disclosure, but is made for the purpose of illustrating the general principles of the disclosure and not for the purpose of limiting the scope of the disclosure. The scope of the disclosure is to be determined by the claims appended hereto.
For the purpose of facilitating an understanding of the embodiments of the present disclosure, the following detailed description is to be construed in conjunction with the accompanying drawings, and the various drawings are not intended to limit the embodiments of the present disclosure.
In one embodiment, as shown in fig. 1, the present disclosure provides a method for manufacturing a bismuth telluride thermoelectric device, including the following steps:
s100: selecting a proper amount of Ni powder raw material and C powder raw material, mixing and then ball-milling to obtain Ni-C mixed powder;
s200: filling a proper amount of bismuth telluride powder into the grinding tool and prepressing to form a bismuth telluride thermoelectric material layer;
s300: drying the Ni-C mixed powder, filling the dried Ni-C mixed powder into a grinding tool, and uniformly accumulating the powder on the bismuth telluride thermoelectric material layer for secondary prepressing to form a Ni-C barrier layer;
s400: and sintering the bismuth telluride thermoelectric material layer and the Ni-C barrier layer to obtain the bismuth telluride thermoelectric device.
In the embodiment, the C raw material is selected to partially replace a Ni raw material, so that the diffusion and reaction of Ni and Te elements in reaction layers at the interfaces of the bismuth telluride hot spot material layer and the barrier layer can be reduced to a certain extent, the good interface resistance and bonding strength of Ni serving as the barrier layer can be retained, the service performance of the device at low temperature can be improved, and the degradation of the interfaces of the bismuth telluride thermoelectric material layer and the pure Ni barrier layer can be inhibited to a certain extent.
Hereinafter, the embodiments of the present disclosure will be described in detail with reference to specific examples.
In one embodiment, a method of fabricating a bismuth telluride thermoelectric device includes the steps of:
1. weighing 4g of Ni powder raw material with the purity of 99.99 percent and 1g of C powder with the purity of 99.99 percent, putting the raw materials and the C powder into a ball mill for ball milling, and adding absolute ethyl alcohol into a ball milling tank to obtain Ni-C mixed powder;
in this step, if too much Ni powder is doped, the contact interface between the barrier layer and the thermoelectric material layer can react more easily to generate Ni x Te y And if the excessively doped C powder affects the conductivity and the thermal expansion coefficient of the barrier layer, the two conditions are not favorable for the stability of the interface, so that the two conditions can be avoided by selecting the Ni powder and the C powder with the volume of 1: 1, and when the volume of the Ni powder and the C powder is 1: 1, the mass ratio of the Ni powder raw material to the C powder raw material is calculated to be 4:1 according to the density of Ni and C.
In addition, the total rotational speed of ball mill is 500rpm, and the spinning disk rotational speed is 800rpm, and the revolution dish rotational speed is 300rpm, and ball-milling processing mode adopts intermittent type nature ball-milling, and every ball-milling 2h pause 0.5h promptly, and ball-milling total time is 8h, through intermittent type nature ball-milling, can prevent on the one hand that the powder is stained with the wall and influence ball-milling efficiency, and on the other hand can protect the motor for the motor can be run for a long time and from not influencing ball-milling efficiency.
2. Weighing 4g of P-type bismuth telluride powder, filling the powder into a graphite grinding tool with the diameter of 1cm, and pre-pressing the powder under the pressure of 20MPa to form a P-type bismuth telluride thermoelectric material layer;
3. weighing 3g of Ni-C mixed powder, drying in a vacuum drying oven with the vacuum degree of less than or equal to 0.1Pa and the temperature of 80 ℃ for 18h, filling into a grinding tool, uniformly accumulating on the P-type bismuth telluride thermoelectric material layer, and performing secondary pre-pressing under the pressure of 20MPa to form a Ni-C barrier layer;
4. and performing SPS sintering on the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer, wherein in the sintering process, the temperature is firstly raised to 300 ℃, the pressure is maintained at 45MPa for 15min, then the temperature is raised to 500 ℃, the pressure is maintained for 10min, then the material is naturally cooled, and the P-type bismuth telluride thermoelectric device can be obtained after cooling.
In another embodiment, a method of fabricating a bismuth telluride thermoelectric device includes the steps of:
1. weighing 4g of Ni powder raw material with the purity of 99.99 percent and 1g of C powder with the purity of 99.99 percent, putting the raw materials and the C powder into a ball mill for ball milling, and adding absolute ethyl alcohol into a ball milling tank to obtain Ni-C mixed powder;
in the step, the total rotating speed of the ball mill is 500rpm, the rotating speed of the self-rotating disc is 800rpm, the rotating speed of the revolution disc is 300rpm, and the ball milling treatment mode adopts intermittent ball milling, namely, 2.5h of ball milling is stopped for 0.5h, and the total ball milling time is 9h.
2. Weighing 4g of P-type bismuth telluride powder, filling the powder into a graphite grinding tool with the diameter of 1cm, and pre-pressing the powder under the pressure of 25MPa to form a P-type bismuth telluride thermoelectric material layer;
3. weighing 3g of Ni-C mixed powder, drying the Ni-C mixed powder in a vacuum drying oven with the vacuum degree of less than or equal to 0.1Pa and the temperature of 90 ℃ for 19h, filling the dried powder into a grinding tool, uniformly accumulating the powder on the P-type bismuth telluride thermoelectric material layer, and performing secondary pre-pressing under the pressure of 25MPa to form a Ni-C barrier layer;
4. and (3) performing SPS sintering on the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer, wherein in the sintering process, the temperature is increased to 300 ℃, the pressure is maintained at 47MPa for 15min, then the temperature is increased to 500 ℃, the pressure is maintained for 10min, then the material is naturally cooled, and the P-type bismuth telluride thermoelectric device can be obtained after cooling.
In the above 2 embodiments, after the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer are sintered, the Ni-C barrier layer is thinned by wire cutting and polishing according to test requirements, the thickness of the thinned Ni-C barrier layer is 0.2mm, a reaction layer at an interface between the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is analyzed by a field emission scanning electron microscope, analysis results are shown in fig. 2 to 4, a contact resistance at the interface is measured by a four-probe method, and a product of the contact resistance and an interface area is an interface resistance.
FIG. 2 is an SEM image of the interface between a Ni-C barrier layer and a P-type bismuth telluride layer aged at 200 ℃ for 100 hours in an air atmosphere, and it can be seen from FIG. 2 that under the aging condition, the measured thickness of the reaction layer between the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is about 10 μm, which is less than the typical value of the thickness of the reaction layer between a pure Ni barrier layer and the P-type bismuth telluride layer, and the smaller the thickness of the reaction layer, the smaller the contact resistance between the P-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is, the better the service stability of the interface is.
FIG. 3 is the contact resistance of a Ni-C barrier layer with P-type bismuth telluride without aging, and FIG. 4 is the contact resistance of a Ni-C barrier layer with P-type bismuth telluride aged at 200 ℃ for 100 hours in an air atmosphere. In FIG. 3, the data points are the contact resistances measured at different positions, and the straight line is the equation of one-time fit line of the data points in the corresponding interval, as can be seen from FIG. 3, the maximum contact resistance between the un-aged Ni-C barrier layer and the P-type bismuth telluride is about 16.3 μ Ω cm 2 . Similarly, in FIG. 4, the contact resistance between the Ni-C barrier layer and the P-type bismuth telluride after aging in an air atmosphere at 200 ℃ for 100 hours is about 17.4. Mu. Omega. Cm at the maximum 2 The contact resistance of the interface between the pure Ni barrier layer and the P-type bismuth telluride, which has been generally used at present, after aging for 100 hours in an air atmosphere at 200 ℃ was measured to be 30. Mu. Omega. Cm 2 In contrast, the difference between the contact resistance of the non-aged Ni-C barrier layer and the P-type bismuth telluride and the contact resistance of the Ni-C barrier layer and the P-type bismuth telluride aged at 200 ℃ for 100 hours in an air atmosphere was 1.1. Mu. Omega. Cm 2 However, the difference of the contact resistance with the interface of the pure Ni barrier layer aged under the same condition and the P-type bismuth telluride is 13.7 mu omega cm 2 Thus, the above description is madeThe scheme has a better improvement effect on the degradation phenomenon at the interface of the bismuth telluride under the condition of 200 ℃.
In another embodiment, a method of fabricating a bismuth telluride thermoelectric device includes the steps of:
1. weighing 4g of Ni powder raw material with the purity of 99.99 percent and 1g of C powder with the purity of 99.99 percent, putting the raw materials and the C powder into a ball mill for ball milling, and adding absolute ethyl alcohol into a ball milling tank to obtain Ni-C mixed powder;
in this step, the mass ratio of the Ni powder raw material to the C powder raw material was also 4:1 for the reasons described above. The total rotating speed of the ball mill is 500rpm, the rotating speed of the self-rotating disc is 800rpm, the rotating speed of the revolution disc is 300rpm, and the ball milling treatment mode adopts intermittent ball milling, namely 3 hours of ball milling is stopped for 0.5 hour, and the total ball milling time is 10 hours.
2. Weighing 4g of N-type bismuth telluride powder, filling the N-type bismuth telluride powder into a graphite grinding tool with the diameter of 1cm, and pre-pressing the powder under the pressure of 28MPa to form an N-type bismuth telluride thermoelectric material layer;
3. weighing 3g of Ni-C mixed powder, drying the Ni-C mixed powder in a vacuum drying oven with the vacuum degree of less than or equal to 0.1Pa and the temperature of 95 ℃ for 20h, filling the dried powder into a grinding tool, uniformly accumulating the powder on the N-type bismuth telluride thermoelectric material layer, and performing secondary pre-pressing under the pressure of 28MPa to form a Ni-C barrier layer;
4. and (3) performing SPS sintering on the N-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer, wherein in the sintering process, the temperature is increased to 300 ℃, the pressure is maintained at 48MPa for 15min, then the temperature is increased to 500 ℃, the pressure is maintained for 10min, then the natural cooling is performed, and the N-type bismuth telluride thermoelectric device can be obtained after the cooling.
In another embodiment, a method of fabricating a bismuth telluride thermoelectric device includes the steps of:
1. weighing 4g of Ni powder raw material with the purity of 99.99 percent and 1g of C powder with the purity of 99.99 percent, putting the raw materials and the C powder into a ball mill for ball milling, and adding absolute ethyl alcohol into a ball milling tank to obtain Ni-C mixed powder;
in the step, the mass ratio of the Ni powder raw material to the C powder raw material is also 4:1, because as mentioned above, the total rotation speed of the ball mill is 500rpm, the rotation speed of the self-rotating disc is 800rpm, the rotation speed of the revolution disc is 300rpm, the ball milling treatment mode adopts intermittent ball milling, namely, 4 hours of pause are performed every time the ball milling is performed, and the total time of the ball milling is 12 hours.
2. Weighing 4g of bismuth telluride powder N, filling the powder N into a graphite grinding tool with the diameter of 1cm, and pre-pressing the powder N under the pressure of 30MPa to form a bismuth telluride thermoelectric material layer N;
3. weighing 3g of Ni-C mixed powder, drying in a vacuum drying oven with the vacuum degree of less than or equal to 0.1Pa and the temperature of 100 ℃ for 20h, filling into a grinding tool, uniformly accumulating on the N-type bismuth telluride thermoelectric material layer, and performing secondary pre-pressing under the pressure of 30MPa to form a Ni-C barrier layer;
4. and (3) performing SPS sintering on the N-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer, wherein in the sintering process, the temperature is increased to 300 ℃, the pressure is maintained at 50MPa for 15min, then the temperature is increased to 500 ℃, the pressure is maintained for 10min, then the natural cooling is performed, and the N-type bismuth telluride thermoelectric device can be obtained after the cooling.
In the 2 embodiments, after the sintering of the N-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is completed, the Ni-C barrier layer needs to be thinned by wire cutting and polishing according to test requirements, the thickness of the thinned Ni-C barrier layer is 0.5mm, the interface between the N-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is analyzed by a field emission scanning electron microscope, the analysis result is shown in fig. 5 to 7, the contact resistance at the interface is measured by a four-probe method, and the product of the contact resistance and the interface area is the interface resistance.
FIG. 5 is an SEM image of the interface of a Ni-C barrier layer and a bismuth N-telluride layer aged at 150 deg.C in an air atmosphere for 15 days, from FIG. 5 it can be seen that under this aged condition the measured thickness of the reaction layer of the thermoelectric material layer of bismuth N-telluride and the Ni-C barrier layer is about 10 μm, less than the typical value of the thickness of the reaction layer of a pure Ni barrier layer and bismuth N-telluride. The smaller the thickness of the reaction layer is, the smaller the contact resistance between the N-type bismuth telluride thermoelectric material layer and the Ni-C barrier layer is, and the better the service stability of the interface is.
FIG. 6 is the contact resistance of a Ni-C barrier layer with bismuth N-telluride without aging, and FIG. 7 is the contact resistance of a Ni-C barrier layer with bismuth N-telluride aged at 150 ℃ for 15 days in an air atmosphere. In FIG. 6, the data points are the contact resistances measured at different positions, and the straight line is the one-time equation fit line of the data points in the corresponding interval, as can be seen from FIG. 6, the un-aged Ni-C barrier layer and the N-typeThe maximum contact resistance of bismuth telluride is about 59.6 mu omega cm 2 In FIG. 7, the contact resistance between the Ni-C barrier layer and the N-type bismuth telluride aged at 150 ℃ for 15 days in the air atmosphere is about 50.8. Mu. Omega. Cm at the maximum 2 The contact resistance of the interface of the Co-P barrier layer with better effect and the N-type bismuth telluride after aging for 15 days at 150 ℃ in the air atmosphere is 80 mu omega cm 2 In contrast, the contact resistance between the Ni-C barrier layer without aging and the bismuth N-telluride was different by 8.8. Mu. Omega. Cm from the contact resistance between the Ni-C barrier layer aged at 150 ℃ in an air atmosphere for 15 days and the bismuth N-telluride 2 However, the difference between the thickness and the contact resistance at the interface between the Co-P barrier layer and the bismuth N-telluride layer aged under the same conditions was 20.4. Mu. Omega. Cm 2 Therefore, the scheme has a better improvement effect on the degradation phenomenon at the bismuth telluride interface under the condition of 150 ℃.
The foregoing description of the present disclosure has been presented with specific examples to aid understanding thereof, and is not intended to limit the present disclosure. Any partial modification or replacement within the technical scope disclosed in the present disclosure by a person skilled in the art should be included in the scope of the present disclosure.

Claims (7)

1. A method for preparing a bismuth telluride thermoelectric device comprises the following steps:
s100: mixing and ball-milling a Ni powder raw material with the purity of 99.99% and a C powder raw material with the purity of 99.99% in a mass ratio of 4;
s200: filling a proper amount of bismuth telluride powder into the grinding tool and prepressing to form a bismuth telluride thermoelectric material layer;
s300: drying the Ni-C mixed powder, filling the dried Ni-C mixed powder into a grinding tool, and uniformly accumulating the dried Ni-C mixed powder on the bismuth telluride thermoelectric material layer for secondary prepressing to form a Ni-C barrier layer;
s400: and performing SPS sintering on the bismuth telluride thermoelectric material layer and the Ni-C barrier layer, wherein in the sintering process, the temperature is firstly raised to 300 ℃, the pressure is maintained at 45-50MPa for 15min, then the temperature is raised to 500 ℃, the pressure is maintained for 10min, and then the bismuth telluride thermoelectric device is obtained by natural cooling.
2. The method of claim 1, wherein the ball milling in step S100 is intermittent ball milling, the ball milling is stopped for 0.5h after 2-4h, and the ball milling time is 8-12h.
3. The method according to claim 1, wherein the bismuth telluride powder is pre-pressed and the Ni-C mixed powder is secondarily pre-pressed at a pressure of 20 to 30MPa in steps S200 and S300.
4. The method of claim 1, wherein in step S200, the Ni-C mixed powder is dried for 18-20h in an environment with a vacuum degree of 0.1Pa or less and a temperature of 80-100 ℃.
5. The method of claim 1, wherein in step S400, after the bismuth telluride thermoelectric material layer and the Ni-C barrier layer are sintered, the Ni-C barrier layer is thinned.
6. The method according to claim 5, wherein the thickness of the Ni-C barrier layer after thinning treatment is 0.2mm to 0.5mm.
7. The method of claim 1, wherein in step S300, the barrier layer comprises 80wt% Ni powder and 20wt% C powder.
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