CN116693292A - p-type Bi 2 Te 3 Method for preparing base thermoelectric material - Google Patents

p-type Bi 2 Te 3 Method for preparing base thermoelectric material Download PDF

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CN116693292A
CN116693292A CN202310661743.2A CN202310661743A CN116693292A CN 116693292 A CN116693292 A CN 116693292A CN 202310661743 A CN202310661743 A CN 202310661743A CN 116693292 A CN116693292 A CN 116693292A
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ball milling
temperature
powder
thermoelectric material
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吴翊
何海龙
虞珂
纽春萍
荣命哲
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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Abstract

Discloses a p-type Bi 2 Te 3 The preparation method of the base thermoelectric material and the thermoelectric material comprise the following steps: the simple substances Bi, cu, sb and Te are used as raw materials, and the chemical formula Bi of the thermoelectric material is adopted 0.5 Cu 2x Sb 1.5 Te 3+x Weighing, mixing and putting into a ball milling tank, wherein the value range of x is 0-0.15; ball milling the raw materials in the ball milling tank by a ball mill to obtain powder; the powder after ball milling is true by adopting SPS sintering methodSintering under air pressurizing condition to form p-type Bi 2 Te 3 A thermoelectric material. The method remarkably improves the conductivity, and can obtain micro-nano powder with different dimensions through a high-energy ball milling combined SPS sintering process.

Description

p-type Bi 2 Te 3 Method for preparing base thermoelectric material
Technical Field
The present disclosure relates to thermoelectric materials, and more particularly to a p-type Bi 2 Te 3 A method for preparing a thermoelectric material.
Background
Thermoelectric materials are functional materials that enable the conversion of thermal and electrical energy. Thermoelectric conversion technology is based on the Seebeck effect, and thermoelectric electromotive force is formed by migration of carriers driven by temperature difference, so that mutual conversion of heat energy and electric energy can be realized. The thermoelectric power generation device made of thermoelectric materials can utilize industrial waste heat, geothermal heat, human body temperature and the like as heat sources to perform thermoelectric conversion, and has the advantages of small volume, high stability, long service life, environmental protection, no maintenance and the like. The energy problem and the environmental problem are increasingly serious in the world today, the energy resource is fully utilized, and the improvement of the energy utilization efficiency becomes the current research thermoelectric. The thermoelectric conversion technology can realize the conversion from low-grade heat sources, waste heat and waste heat to electric energy, and has wide application prospect in the field of energy resource utilization.
The thermoelectric figure of merit (dimensionless ZT value) is an indicator that measures thermoelectric conversion efficiency of a thermoelectric material. Thermoelectric materials with high thermoelectric conversion efficiency tend to have large thermoelectric figure of merit. ZT can be expressed as:
where S is the seebeck coefficient, which is the electromotive force generated at the unit gradient temperature of a material, and the magnitude depends on the carrier type and the temperature difference across the material. σ is conductivity, which is related to carrier concentration and carrier mobility. Kappa is the thermal conductivity, which is defined by the electrical conductivityRate and lattice thermal conductivity. Thermoelectric materials with higher thermoelectric figure of merit often have higher seebeck coefficients, higher electrical conductivities and lower thermal conductivities, but the relationship among the three is mutual coupling, mutual influence and difficult comprehensive regulation. Bi (Bi) 2 Te 3 The base thermoelectric material is a thermoelectric material suitable for low temperature (room temperature-300 ℃), and the material has been commercially applied at present. Commercial p-type Bi 2 Te 3 The conductivity of the material at room temperature is typically 10 5 S/m or so, commercial p-type Bi in certain applications with higher conductivity requirements 2 Te 3 The conductivity of the material is slightly insufficient, so that the p-type Bi is improved for the use scenes 2 Te 3 The electrical conductivity of the thermoelectric material is one of the problems that needs to be solved at present.
The above information disclosed in the background section is only for enhancement of understanding of the background of the application and therefore may contain information that does not form the prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
In view of the deficiencies in the prior art, an object of the present disclosure is to provide a p-type Bi of high conductivity 2 Te 3 A method for preparing a base thermoelectric material.
In order to achieve the above object, the present disclosure provides the following technical solutions:
p-type Bi 2 Te 3 The preparation method of the base thermoelectric material comprises the following steps:
the simple substances Bi, cu, sb and Te are used as raw materials, and the chemical formula Bi of the thermoelectric material is adopted 0.5 Cu 2x Sb 1.5 Te 3+x Weighing, mixing and putting into a ball milling tank, wherein the value range of x is 0-0.15;
ball milling the raw materials in the ball milling tank by a ball mill to obtain powder;
sintering the powder after ball milling by adopting an SPS sintering method under vacuum pressurization to form p-type Bi 2 Te 3 A thermoelectric material.
In the method, powder after ball milling is subjected to SPS sintering under the protection of argon atmosphere in a vacuum glove box.
In the method, the ball milling tank and the grinding ball are made of stainless steel, and the grinding aid is absolute ethyl alcohol; the ball milling tank after mixing is vacuumized and sealed.
In the method, the ball mill is a planetary ball mill.
In the method, the total rotating speed of the planetary ball mill is 500rpm, the rotating speed of the rotating disc is 1000rpm, and the rotating speed of the revolution disc is 500rpm.
In the method, a ball mill performs intermittent ball milling; the intermittent ball milling is performed for 15min after each ball milling for 40min, and the total ball milling time is 8h.
In the method, the powder after ball milling is dried in a vacuum drying box, the vacuum degree is less than or equal to 0.1Pa, the drying temperature is 70-100 ℃, and the drying time is more than or equal to 18 hours.
In the method, the temperature of the vacuum dry box is raised by adopting gradient; and the gradient temperature is increased to 70 ℃ for 30min, the temperature is kept for 5h, then the temperature is increased to 100 ℃ for 2h, and the temperature is kept continuously.
In the method, the dried powder material is screened by using an ultrasonic vibration screen; the number of the vibration sieves is more than or equal to 450 meshes.
p-type Bi 2 Te 3 The thermoelectric material is prepared according to the method.
Compared with the prior art, the beneficial effects that this disclosure brought are: the thermoelectric material is prepared by combining a high-energy ball milling method with SPS sintering. The high-energy ball milling can greatly reduce the preparation period of powder, and the vacuumizing sealing can effectively prevent the volatilization of raw materials after the ball milling process. The SPS sintering speed is high, the density of the sintered block material is good, and the preparation efficiency of the thermoelectric material is greatly improved. The method can rapidly and efficiently prepare Bi 0.5 Cu 2x Sb 1.5 Te 3+x Where x is determined by the specific gravity of Cu element in the total mass, a typical value is 0.032,0.065,0.13. The proper value range of x is 0-0.15, if x is too small, the performance regulation effect is limited, the regulation effect gradually approaches saturation along with the increase of the value of x, and if x exceeds 0.15, the change amount of the performance parameters is small. The addition of the additional Cu element can obviously improve the conductivity, and the S is combined by high-energy ball millingThe PS sintering process can obtain micro-nano powder with different dimensions. Sample Bi when x=0.065 0.5 Cu 0.13 Sb 1.5 Te 3.065 At a temperature of 308K, the electrical conductivity is as high as 2.7X10 5 S/m is currently commercial p-type Bi 2 Te 3 Conductivity of the thermoelectric material (at 10 5 S/m) is 2 times or more. Bi prepared by the application 0.5 Cu 2x Sb 1.5 Te 3+x The thermoelectric material has better application prospect in the occasion with higher requirements on conductivity in the middle-low temperature range.
Drawings
FIG. 1 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 A thermoelectric material preparation process flow chart;
FIG. 2 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 SEM image of thermoelectric material;
FIG. 3 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 A graph of the seebeck coefficient of the thermoelectric material versus temperature;
FIG. 4 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 A plot of thermoelectric material conductivity versus temperature;
FIG. 5 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 A graph of thermoelectric material power factor versus temperature;
FIG. 6 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 A graph of thermoelectric material thermal conductivity versus temperature;
FIG. 7 shows the p-type Bi mentioned in the examples 0.5 Cu 0.13 Sb 1.5 Te 3.065 Thermoelectric material ZT value versus temperature.
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 claims to refer to particular components. Those of skill in the art will understand that a person may refer to the same component by different names. The specification and claims do not identify differences in terms of components, but rather differences in terms of the functionality of the components. As used throughout the specification and 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 hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description proceeds with reference to the general principles of the description. The scope of the present disclosure is defined by the appended claims.
For the purposes of promoting an understanding of the embodiments of the disclosure, reference will now be made to the embodiments illustrated in the drawings and specific examples, without the intention of being limiting the embodiments of the disclosure.
As shown in fig. 1 to 7, a p-type Bi 2 Te 3 The preparation method of the base thermoelectric material comprises the following steps:
the simple substances Bi, cu, sb and Te are used as raw materials, and the chemical formula Bi of the thermoelectric material is adopted 0.5 Cu 2x Sb 1.5 Te 3+x The materials are weighed and mixed, and put into a ball milling tank, wherein x is determined according to the proportion of Cu element in the total mass, and a typical value is 0.032,0.065,0.13. The proper value range of x is 0-0.15, if x is too small, the performance regulation effect is limited, the regulation effect gradually approaches saturation along with the increase of the value of x, and if x exceeds 0.15, the change amount of the performance parameters is small;
ball milling the raw materials in the ball milling tank by a ball mill to obtain powder;
sintering the powder after ball milling by adopting an SPS sintering method under vacuum pressurization to form p-type Bi 2 Te 3 A thermoelectric material.
In a preferred embodiment of the method, the powder after ball milling is subjected to SPS sintering under the protection of argon atmosphere in a vacuum glove box.
In the preferred embodiment of the method, the ball milling tank and the grinding ball are made of stainless steel, and the grinding aid is absolute ethyl alcohol; the ball milling tank after mixing is vacuumized and sealed.
In a preferred embodiment of the method, the ball mill is a planetary ball mill.
In a preferred embodiment of the method, the total rotation speed of the planetary ball mill is 500rpm, the rotation speed of the rotating disc is 1000rpm, and the rotation speed of the revolving disc is 500rpm.
In a preferred embodiment of the method, the ball mill is operated intermittently; the intermittent ball milling is performed for 15min after each ball milling for 40min, and the total ball milling time is 8h.
In the preferred embodiment of the method, the powder after ball milling is dried in a vacuum drying box, the vacuum degree is less than or equal to 0.1Pa, the drying temperature is 70-100 ℃, and the drying time is more than or equal to 18 hours.
In a preferred embodiment of the method, the temperature of the vacuum drying box is raised by gradient; and the gradient temperature is increased to 70 ℃ for 30min, the temperature is kept for 5h, then the temperature is increased to 100 ℃ for 2h, and the temperature is kept continuously.
In a preferred embodiment of the method, the dried powder material is sieved by using an ultrasonic vibration sieve; the number of the vibration sieves is more than or equal to 450 meshes.
In a preferred embodiment of the method, the SPS sintering initial temperature is room temperature, and the sintering temperature is 350-450 ℃; the pressure is 50-65 MPa; the incubation time was 10min.
In one embodiment, the material is prepared having the chemical formula Bi 0.5 Cu 2x Sb 1.5 Te 3+x Where x is determined by the specific gravity of Cu element in the total mass, a typical value is 0.032,0.065,0.13. The proper value range of x is 0-0.15, if x is too small, the performance regulation effect is limited, the regulation effect gradually approaches saturation along with the increase of the value of x, and if x exceeds 0.15, the change amount of the performance parameters is small.The p-type Bi 2 Te 3 The preparation method of the base thermoelectric material comprises the following steps:
(1) The simple substance raw materials of Bi, cu, sb and Te are weighed according to the component proportion and are put into ball milling;
(2) Powder preparation, namely placing a ball milling tank on a planetary ball mill for ball milling for 8 hours by adopting a powder preparation method of high-energy ball milling;
(3) Powder treatment, namely sieving and vacuum drying the powder after ball milling;
(4) And sintering the block, and placing the dried powder into an SPS sintering furnace for sintering.
In the component proportioning step, raw material weighing is carried out in a glove box protected by argon atmosphere. According to the chemical formula Bi 0.5 Cu 2x Sb 1.5 Te 3+x Namely according to the mass ratio Bi: cu: sb: te= 104.49:127.09x:182.55: (382.8+127.6x) weighing simple substance raw materials in a glove box, putting the simple substance raw materials into a stainless steel ball grinding tank, wherein grinding balls with three specifications of large, medium and small are arranged in the ball grinding tank, the grinding balls have the specification of phi 20mm grinding balls of 80.23g, phi 15mm grinding balls of 78.95g, phi 8mm grinding balls of 60.86g, phi 6mm grinding balls of 80.8g and phi 4mm grinding balls of 30.68g, the total mass of the grinding balls is 331.52g, the mass of powder is controlled to be 10 g-20 g, and the ball-to-material ratio is 1:30 or less. And (3) pouring absolute ethyl alcohol into the ball milling tank, wherein the dosage of the absolute ethyl alcohol slightly exceeds that of all the fillers, but the liquid level of the absolute ethyl alcohol is ensured not to exceed 1/3 of the volume of the ball milling tank. After all the materials are filled, the ball milling tank is put into a glove box transition bin, vacuum sealing is carried out, and then the ball milling tank is taken out for ball milling treatment.
In the powder preparation process, the selected ball milling treatment mode is intermittent ball milling, wherein the intermittent ball milling is performed for 15min after each ball milling for 40min, and the total ball milling time is 8h. Intermittent ball milling is used for preventing powder from being stained with walls to influence ball milling efficiency and protecting a motor. Setting the working parameters of the ball mill as follows: the total rotation speed of the ball mill is 500rpm, the rotation speed of the rotating disc is 1000rpm, and the rotation speed of the revolution disc is 500rpm. The powder after ball milling is subjected to vacuum drying treatment. The vacuum degree of the drying oven is less than or equal to 0.1Pa, the temperature is raised to 70 ℃ for 30min, the heat is preserved for 5h, then the temperature is raised to 100 ℃ for 2h, and the heat is preserved continuously. The total heat preservation time is more than 18 hours. Adopts a gradient heating mode, and aims to volatilize ethanol liquid under the current low-temperature vacuum condition, and then dry the rest powder completely at high temperature. The dried powder material is screened by an ultrasonic vibration screen, and the number of the vibration screen is more than or equal to 450 meshes. Sieving separates powders with different particle sizes, and can screen out impurities with larger particle sizes.
In the bulk sintering process, SPS sintering is selected, and in an alternative embodiment, SPS sintering parameters include: the initial temperature is room temperature, and the sintering temperature is 350-450 ℃; the pressure is 50-65 MPa; the incubation time was 10min. Gradient heating is adopted in the sintering process, and pressure is maintained in the whole process; the gradient heating is carried out, the whole pressure maintaining is carried out for 10min, the temperature is increased to 250 ℃ from room temperature, then the temperature is increased to 450 ℃ for 5min, the temperature is kept for more than 10min, and then the furnace cooling is carried out; the whole sintering process keeps pressure uploading.
In the application, the defects of the traditional synthesis method can be well avoided by adopting high-energy ball milling and SPS sintering processes. The high-energy ball milling does not need high-temperature reaction conditions, so that the problem that the vapor pressure is too high due to vaporization of reaction raw materials is avoided, and potential safety hazards are brought. Compared with the conventional melting method which requires longer heat preservation time and annealing time and generally requires 10 days or more, the preparation period of the material can be greatly reduced by combining the high-energy ball milling with the SPS sintering process, and the preparation efficiency is improved. In addition, the melting method can prepare nano-scale powder, so that scattering of phonons with short wavelength can be enhanced, and the high-energy ball milling combined with SPS sintering technology can prepare micro-nano-scale full-scale powder, so that the nano-scale powder has good scattering effect on phonons with short wavelength and long wavelength, and the thermal conductivity of the material can be further reduced.
Preferably, the raw material weighing is performed in a glove box protected by argon atmosphere.
Preferably, the ball milling tank and the grinding ball are made of stainless steel, and the grinding aid is absolute ethyl alcohol.
Preferably, the ball milling tank after mixing is required to be vacuumized and sealed before ball milling.
Preferably, the ball milling treatment mode is intermittent ball milling. The intermittent ball milling is performed for 15min after each ball milling for 40min, and the total ball milling time is 8h. Intermittent ball milling is used for preventing powder from being stained with walls to influence ball milling efficiency and protecting a motor.
Preferably, the total rotation speed of the ball mill is 500rpm, the rotation speed of the rotating disc is 1000rpm, and the rotation speed of the revolution disc is 500rpm.
Preferably, the powder after ball milling is subjected to vacuum drying treatment. The vacuum degree of the drying oven is less than or equal to 0.1Pa, the temperature is raised to 70 ℃ for 30min, the heat is preserved for 5h, then the temperature is raised to 100 ℃ for 2h, and the heat is preserved continuously. The total heat preservation time is more than 18 hours. Adopts a gradient heating mode, and aims to volatilize ethanol liquid under the current low-temperature vacuum condition, and then dry the rest powder completely at high temperature.
Preferably, the dried powder material is screened by using an ultrasonic vibration screen, and the vibration screen with the mesh number more than or equal to 450 meshes is selected. The powder with different particle sizes can be separated by sieving, and impurities with larger particle sizes can be removed by sieving.
On the other hand, the application also provides the p-type Bi prepared by the preparation method 2 Te 3 A thermoelectric material.
In yet another aspect, the present application also provides a p-type Bi 2 Te 3 Compact block of base thermoelectric material, p-type Bi as described above 2 Te 3 The p-type Bi is obtained by SPS sintering of the base thermoelectric material serving as a raw material 2 Te 3 A dense block of base thermoelectric material; SPS sintering parameters are: the initial temperature is room temperature, and the sintering temperature is 350-450 ℃; the pressure is 50-65 MPa; the incubation time was 10min. Gradient heating is adopted in the sintering process, and pressure is maintained in the whole process; the gradient heating is carried out, the whole pressure maintaining is carried out for 10min, the temperature is increased to 250 ℃ from room temperature, then the temperature is increased to 450 ℃ for 5min, the temperature is kept for more than 10min, and then the furnace cooling is carried out; the whole sintering process keeps pressure uploading.
Examples
Taking x value as 0.065 to prepare p-type Bi 0.5 Cu 0.13 Sb 1.5 Te 3.065 Thermoelectric materials. 2.6123g of Bi simple substance raw material, 0.2065g of Cu simple substance raw material, 4.5638g of Sb simple substance raw material and 9.7774g of Te simple substance raw material are weighed in proportion in an argon atmosphere glove box and filled into a stainless steel ball grinding tank.
The stainless steel ball milling tank is vacuumized and sealed in a transition bin, and then taken out for high-energy ball milling. In the embodiment, the revolution disc speed of the ball mill is 1000rpm, the rotation disc speed is 500rpm, an intermittent ball milling mode is adopted, the ball milling is stopped for 15min after each ball milling time of 40min, and the total ball milling time is 30h. And taking out the powder after ball milling, and putting the powder into a vacuum drying oven for drying. The vacuum degree of the drying oven is less than or equal to 0.1Pa, the temperature is raised to 70 ℃ for 30min, the heat is preserved for 5h, then the temperature is raised to 100 ℃ for 2h, and the heat is preserved for 16h continuously. And taking out the dried powder, sieving with a 450-mesh sieve, and weighing a proper amount of powder and pressing into a block material with phi of 20 multiplied by 3 mm.
And (3) placing the pressed material into an SPS sintering furnace, and performing pressure sintering in a vacuum state. The sintering temperature was 450℃and the applied pressure during sintering was 50MPa. The sintering process adopts a gradient heating and pressure maintaining mode, firstly, the temperature is raised to 250 ℃ from room temperature for 10min, then the temperature is raised to 450 ℃ for 5min, the temperature is kept for more than 10min, and then the furnace is cooled; the whole sintering process is carried out under the pressure of 50Mpa.
Seebeck coefficient and electric conductivity are measured by a ZEM-3 thermoelectric performance analysis system, and the thermal conductivity is further calculated by the thermal diffusion coefficient of an LFA-467 laser thermal conductivity meter, so that the prepared p-type Bi can be finally calculated 0.5 Cu 0.13 Sb 1.5 Te 3.065 The power factor and ZT value of the thermoelectric material. As shown in fig. 3, 4, 5, 6, and 7, bi when t=308K 0.5 Cu 0.13 Sb 1.5 Te 3.06 The seebeck coefficient of the thermoelectric block is 0.00011V/K, and the conductivity is 2.7X10 5 S/m, power factor of 35W/mK 2 The thermal conductivity was 1.9W/mK, and the ZT value was 0.68.
The basic principles of the present disclosure have been described above in connection with specific embodiments, however, it should be noted that the advantages, benefits, effects, etc. mentioned in the present disclosure are merely examples and not limiting, and these advantages, benefits, effects, etc. are not to be considered as necessarily possessed by the various embodiments of the present disclosure. Furthermore, the specific details disclosed herein are for purposes of illustration and understanding only, and are not intended to be limiting, as the application is not necessarily limited to practice with the above described specific details.

Claims (10)

1. P-type Bi 2 Te 3 The preparation method of the base thermoelectric material is characterized by comprising the following steps:
the simple substances Bi, cu, sb and Te are used as raw materials, and the chemical formula Bi of the thermoelectric material is adopted 0.5 Cu 2x Sb 1.5 Te 3+x Weighing, mixing and putting into a ball milling tank, wherein the value range of x is 0-0.15;
ball milling the raw materials in the ball milling tank by a ball mill to obtain powder;
sintering the powder after ball milling by adopting an SPS sintering method under vacuum pressurization to form p-type Bi 2 Te 3 A thermoelectric material.
2. The method according to claim 1, wherein the powder after ball milling is preferably subjected to SPS sintering under the protection of argon atmosphere in a vacuum glove box.
3. The method of claim 1, wherein the ball milling tank and the ball milling material are both stainless steel and the grinding aid is absolute ethanol; the ball milling tank after mixing is vacuumized and sealed.
4. The method of claim 1, wherein the ball mill is a planetary ball mill.
5. The method according to claim 4, wherein the planetary ball mill has a total rotation speed of 500rpm, a rotation speed of 1000rpm, and a revolution speed of 500rpm.
6. The method of claim 1, wherein the ball mill is operated for intermittent ball milling; the intermittent ball milling is performed for 15min after each ball milling for 40min, and the total ball milling time is 8h.
7. The method of claim 1, wherein the powder after ball milling is dried in a vacuum drying oven at a vacuum degree of less than or equal to 0.1Pa and a drying temperature of 70-100 ℃ for a drying time of more than or equal to 18 hours.
8. The method of claim 7, wherein the vacuum drying oven is warmed up using a gradient; and the gradient temperature is increased to 70 ℃ for 30min, the temperature is kept for 5h, then the temperature is increased to 100 ℃ for 2h, and the temperature is kept continuously.
9. The method of claim 1, wherein the dried powder material is sieved using an ultrasonic vibrating screen; the number of the vibration sieves is more than or equal to 450 meshes.
10. P-type Bi 2 Te 3 A thermoelectric material, characterized in that it is prepared according to the method of any one of claims 1-9.
CN202310661743.2A 2023-06-06 2023-06-06 p-type Bi 2 Te 3 Method for preparing base thermoelectric material Pending CN116693292A (en)

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