CN107681043B - Bismuth telluride-based composite thermoelectric material of flexible thermoelectric device and preparation method thereof - Google Patents
Bismuth telluride-based composite thermoelectric material of flexible thermoelectric device and preparation method thereof Download PDFInfo
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- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 34
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Abstract
The invention relates to a bismuth telluride based composite thermoelectric material and a preparation method thereof, belonging to the field of thermoelectric conversion new energy materials. The material of the invention is graphite (G) and Bi0.5Sb1.5Te3The chemical composition formula of the composite thermoelectric material is x G/Bi0.5Sb1.5Te3Wherein x is second-phase graphite occupying matrix Bi0.5Sb1.5Te3The mass percentage of x is more than or equal to 0 and less than or equal to 0.20 percent. The bismuth telluride based composite thermoelectric material prepared by adopting a powder metallurgy method and an ultrasonic dispersion phase combination method has the advantages that the comprehensive thermoelectric performance ZT value is obviously improved, and the bismuth telluride based composite thermoelectric material can be used as a raw material for preparing and assembling a high-performance flexible thermoelectric device. Meanwhile, the material has the characteristics of abundant and easily obtained raw materials, simple and controllable process, short preparation period, low energy consumption and the like, is suitable for industrial production, and is expected to realize breakthrough in the commercial application of flexible thermoelectric devices.
Description
Technical Field
The invention relates to a semiconductor thermoelectric power generation and refrigeration material, in particular to a bismuth telluride-based composite thermoelectric material applied to a flexible thermoelectric device and a preparation method thereof, belonging to the field of thermoelectric conversion new energy materials.
Background
The thermoelectric device has the advantages of no pollution, no noise, small volume, high reliability and the like, has wide application prospect and potential economic value in the fields of thermoelectric power generation, refrigeration, solar energy, industrial waste heat utilization and the like, and has been successfully applied to high and new technical fields such as deep space exploration, military equipment, IT industry and the like as a special power supply and a high-precision temperature controller2σ T/κ, where α is the Seebeck coefficient, σ is the electrical conductivity, κ is the thermal conductivity, T is the absolute temperatureEAnd lattice thermal conductivity κLI.e. k ═ kE+κL. Theoretically, the thermal conductivity (κ) is reducedE+κL) And improving the electrical conductivity sigma and Seebeck coefficient α of the material, (improving the electrical transmission performance α)2Sigma) can achieve the goal of improving the ZT value, but because of strong electro-acoustic interaction in the thermoelectric material, three parameters of sigma, α and kappa are difficult to be cooperatively regulated and controlled, and how to optimize the electric and thermal transport performance to obtain the high ZT value is a research problem in the field of thermoelectric devices.
On the other hand, as electronic devices are miniaturized and integrated, there is an increasing demand for miniaturized, highly efficient, and long-life flexible thermoelectric power generation and refrigeration devices. The bismuth telluride-based alloy is one of the most mature thermoelectric materials studied at home and abroad, and is also the material with the best thermoelectric property near room temperature. The preparation method comprises molecular beam epitaxy method, zone melting method, mechanical alloying method, pulsed laser deposition method, and magnetismAnd performing a controlled sputtering method and the like, wherein the maximum thermoelectric figure of merit ZT of the obtained p-type bismuth telluride-based material and the obtained n-type bismuth telluride-based material is 0.8-1. At present, the performance optimization research of the bismuth telluride-based thermoelectric material applied to the flexible thermoelectric device has some outstanding problems, such as (1) the thermal conductivity of the bismuth telluride-based thermoelectric material (1.11 W.m)-1·K-1) The high temperature limits the improvement of the thermoelectric performance; and (2) the electric conductivity of the bismuth telluride-based thin film and thick film thermoelectric material is far lower than that of a block material, and the reason is that organic matters volatilize in the heat treatment process to cause loose and porous film structures and reduced density. In the research aspect of the preparation method of the bismuth telluride base film material, the method for preparing the thick film thermoelectric material mainly comprises the following steps: the screen printing method, the ink jet printing method, the dispensing printing method, the electrochemical deposition method and the spin coating method are successively researched and reported, the methods generally have the problems of higher equipment cost, complex operation and the like, and the controllability of the preparation process is poor, and the thermoelectric property of the film material is unstable, so that the large-scale industrial production is difficult to realize. In order to improve the thermoelectric property of the bismuth telluride based film material, researchers have proposed that a proper amount of sintering aid is added to greatly increase the density of the material, so as to improve the conductivity of the material. However, a large amount of chemical reagents are needed for preparing the sintering aid, and part of organic reagents such as hydrazine hydrate, ethanethiol, trioctylphosphine and the like have the problems of high price, toxicity, high requirement on operating environment conditions and the like. Researchers find that the purpose of improving the electric transmission performance can be achieved by compounding a trace amount of inorganic nano second phase (such as SiC) or nano conductive particles (such as Ag, Cu and the like) with the bismuth telluride-based thermoelectric material. However, the doped Cu can greatly improve the thermal conductivity while improving the electrical conductivity, and the comprehensive thermoelectric performance is sometimes even reduced. The nano SiC is generally prepared by a mechanical alloying Method (MA), and the method has the problems of high energy consumption and low product purity, so that the problem of difficult control of performance stability in industrial application is caused. Similarly, the nano conductive particles generally need to be compounded with a matrix material in the form of a metal compound solution or by an electrochemical deposition method, and have the disadvantages of high preparation cost, complex process, high requirements on equipment conditions and the like, so that large-scale industrial production is difficult to realize.
Disclosure of Invention
The invention provides the bismuth telluride based composite thermoelectric material applied to the flexible device and the preparation method thereof for solving the technical problems. Meanwhile, the composite thermoelectric material prepared by the method has low thermal conductivity and high thermoelectric figure of merit, can be used as a raw material for preparing and assembling a high-performance thick film thermoelectric device, and is expected to realize breakthrough in the commercial application of the thick film thermoelectric device.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a bismuth telluride-based composite thermoelectric material applied to a flexible thermoelectric device is composed of x G/Bi0.5Sb1.5Te3G is graphite, wherein x is second-phase graphite in matrix Bi0.5Sb1.5Te3The mass percentage of x is more than or equal to 0 and less than or equal to 0.20 percent.
In the above aspect, x is 0.05%.
The preparation method of the bismuth telluride-based composite thermoelectric material applied to the flexible thermoelectric device is characterized by comprising the following steps of:
1) preparing Bi by adopting a melting annealing and quenching method0.5Sb1.5Te3Ingot of a base material, preparing Bi0.5Sb1.5Te3Crushing and ball-milling a base material ingot to obtain powder with the particle size of 1-5 mu m;
2) grinding industrial grade graphite block into powder, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as x G/Bi0.5Sb1.5Te3A second phase in the composite thermoelectric material;
3) calculating and weighing matrix powder and corresponding graphite powder according to chemical composition, ultrasonically compounding in absolute ethyl alcohol at normal temperature and normal pressure for 10-20 min, centrifuging, and vacuum drying to obtain x G/Bi0.5Sb1.5Te3The composite thermoelectric powder of (3);
4) x G/Bi0.5Sb1.5Te3The composite thermoelectric powder is poured into a stainless steel mold,performing cold pressing to obtain a composite material blank with the thickness of 1-2 mm;
5) and putting the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment to obtain the bismuth telluride based composite thermoelectric material.
In the scheme, Bi in the step 1)0.5Sb1.5Te3The preparation method of the base material ingot comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the dosage of high-purity metal Bi powder, Sb powder and Te powder, sealing the powder in a quartz tube in a vacuum state, placing the quartz tube in a melting furnace, melting and annealing the quartz tube at the temperature of 700-0.5Sb1.5Te3And (5) casting.
In the scheme, the ball milling process parameters in the step 2) are as follows: the ball milling speed is 200-300 r/min, and the ball milling time is 3-5 h.
In the above scheme, the centrifugal process parameters in step 3): the centrifugal speed is 600-1000 r/min, and the centrifugal time is 5-10 min.
In the scheme, the vacuum drying process parameters in the step 3) are as follows: the drying temperature is 40-60 ℃, and the drying time is 1-2 h.
In the above scheme, the dimension of the stainless steel mold in the step 4) is the inner diameter
Outer diameter
Diameter of pressure head
In the scheme, the pressing process parameters in the step 4) are as follows: the pressing pressure is 10-20 MPa.
In the scheme, the heat treatment process parameters in the step 5) are as follows: the heat treatment temperature is 350-450 ℃, the heat treatment time is 1.5-2.5 h, and the heating rate is 2-10 ℃/min.
The invention takes the industrial grade graphite as the raw material, greatly reduces the preparation cost and the equipmentAnd the requirement is met, and the large-scale production is easy to realize. Because a G second phase is introduced, a large number of crystal boundaries enhance a phonon scattering mechanism, and the lattice thermal conductivity kappa of the bismuth telluride based material can be effectively reducedLAnd the comprehensive thermoelectric performance ZT value of the prepared composite thermoelectric material is obviously improved.
The invention has the beneficial effects that: the method for preparing the bismuth telluride based composite thermoelectric material has the characteristics of simple and controllable process, short preparation period, low energy consumption and the like, and is easy for large-scale industrial production. The composition prepared in the invention is x G/Bi0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%), has the characteristics of abundant and easily available raw materials and excellent hot spot performance, and can stably work at room temperature to 100 ℃. The composition obtained as in example 1 was 0.05% G/Bi0.5Sb1.5Te3The thermal conductivity of the composite thermoelectric material is only 0.40 W.m at room temperature-1·K-1The conductivity and the seebeck coefficient are respectively 3.04 x 104S·m-1And 228.5. mu.V.K-1Finally, the integrated thermoelectric figure of merit ZT reaches 1.05 at 320K.
Drawings
FIG. 1 shows the composition x G/Bi in the present invention0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%) and the data of JCPDS is Bi0.5Sb1.5Te3Standard map data of (JCPDS 49-1713).
FIG. 2 shows 0.05% G/Bi in the present invention0.5Sb1.5Te3BEI image, SEI image and C, Bi, Sb, Te element spectrum scanning map of the composite thermoelectric material.
FIG. 3 shows the composition x G/Bi in the present invention0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%) and a temperature range of 300 to 480K.
FIG. 4 shows the composition x G/Bi in the present invention0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%) of seebeck of the composite thermoelectric materialThe relation curve between the coefficient and the temperature is 300-480K.
FIG. 5 shows the composition x G/Bi in the present invention0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%) and a temperature range of 300 to 480K.
FIG. 6 shows a composition x G/Bi in the present invention0.5Sb1.5Te3(x is 0, 0.05%, 0.10%, 0.15%, 0.20%) and a temperature range of 300 to 480K.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1: 0.05% G/Bi0.5Sb1.5Te3Composite thermoelectric material
Preparation of 0.05% G/Bi in the invention0.5Sb1.5Te3The raw material selection and the specific operation flow of the composite thermoelectric material are as follows:
bi is prepared by adopting a melting annealing and quenching method0.5Sb1.5Te3An ingot of a base material; the preparation method comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the use amounts of high-purity metals Bi (99.99 percent, powder), Sb (99.99 percent, powder) and Te (99.99 percent, powder), sealing the high-purity metals Bi (99.99 percent, powder) into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing for 10 hours at 800 ℃, quenching the melt to obtain a target product Bi0.5Sb1.5Te3The casting block is a base material;
1) and crushing and ball-milling the cast block to obtain matrix powder with the particle size of 1-5 microns. The ball milling process parameters are as follows: the ball milling speed is 200r/min, and the ball milling time is 4 h.
2) Grinding industrial grade graphite block, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as 0.05% G/Bi0.5Sb1.5Te3The second phase graphite raw material in the composite thermoelectric material.
3) According to the chemical composition, 0.05 percent of G/Bi0.5Sb1.5Te3Calculating and weighing 3G of matrix powder and corresponding graphite powder, ultrasonically dispersing the graphite powder in 20ml of absolute ethyl alcohol, adding the matrix powder, ultrasonically dispersing for 15min, centrifuging for 5min at the rotating speed of 800r/min, taking lower-layer slurry, and vacuum drying for 1h at the temperature of 60 ℃ to obtain 0.05% G/Bi0.5Sb1.5Te3Composite thermoelectric powder.
4) Weighing the above 0.05% G/Bi0.5Sb1.5Te31-2 g of composite thermoelectric powder, and pouring into the inner diameter
Outer diameter
Diameter of pressure head
In the stainless steel mold, cold press molding is carried out under 20MPa to obtain a blank body with the thickness of 1-2 mm.
5) Mixing the above 0.05% G/Bi0.5Sb1.5Te3And placing the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment. The heat treatment process parameters are as follows: the heat treatment temperature is 400 ℃, the heat treatment time is 2 hours, and the heating rate is 2-10 ℃/min.
0.05% G/Bi obtained by the above heat treatment0.5Sb1.5Te3The XRD spectrum of the composite material is shown in figure 1 as 0.05% G/Bi0.5Sb1.5Te3The spectral lines show that: main characteristic diffraction peak of composite material sample and standard card JCPDS 49-1713Bi0.5Sb1.5Te3The characteristic diffraction peaks of the compounds are consistent, which shows that the phase composition of the compounds is Bi0.5Sb1.5Te3. This is mainly due to the fact that the second phase, G, is 0.05% much less than the minimum 1% detectable by XRD instrumentation, and therefore no G phase is detected. The spectral profiles of the BEI image, the SEI image, and the C, Bi, Sb, and Te elements are shown in fig. 2: by analyzing and comparing the SEI and BEI images, the gray contrast in the BEI image is the main phase Bi0.5Sb1.5Te3Black contrast is porosity and grain boundaries, which is consistent with XRD results. The results of the spectral surface scan show that: the C element contained in the second phase graphite is uniformly distributed at the crystal boundary position formed by the bismuth telluride matrix crystal grains. The relation curves of the electric conductivity, the Seebeck coefficient, the thermal conductivity and the ZT value of the material under 300-480K and the temperature are shown as 0.05% G/Bi in figures 3-60.5Sb1.5Te3The curves show: at 320K, the power factor is 1.59 mW.m-1K, thermal conductivity as low as 0.48 W.m-1·K-1Finally, the integrated thermoelectric figure of merit ZT reaches a maximum of 1.05.
Example 2: 0.10% G/Bi0.5Sb1.5Te3Composite thermoelectric material
Preparation of 0.10% G/Bi in the present invention0.5Sb1.5Te3The raw material selection and the specific operation flow of the composite thermoelectric material are as follows:
bi is prepared by adopting a melting annealing and quenching method0.5Sb1.5Te3An ingot of a base material; the preparation method comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the use amounts of high-purity metals Bi (99.99 percent, powder), Sb (99.99 percent, powder) and Te (99.99 percent, powder), sealing the high-purity metals Bi (99.99 percent, powder) into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing for 10 hours at 800 ℃, quenching the melt to obtain a target product Bi0.5Sb1.5Te3The casting block is a base material;
1) and crushing and ball-milling the cast block to obtain matrix powder with the particle size of 1-5 microns. The ball milling process parameters are as follows: the ball milling speed is 200r/min, and the ball milling time is 4 h.
2) Grinding industrial grade graphite block, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as 0.10% G/Bi0.5Sb1.5Te3The second phase graphite raw material in the composite thermoelectric material.
3) According to the chemical composition 0.10% G/Bi0.5Sb1.5Te3Calculating and weighing 3g of matrix powder and corresponding graphite powder, ultrasonically dispersing the graphite powder in 20ml of absolute ethyl alcohol, adding the matrix powder, ultrasonically dispersing for 15min, and separating at the rotating speed of 800r/minTaking out the lower layer slurry after 5min, and vacuum drying at 60 deg.C for 1h to obtain 0.10% G/Bi0.5Sb1.5Te3Composite thermoelectric powder.
4) Weighing the above 0.10% G/Bi0.5Sb1.5Te31-2 g of composite thermoelectric powder, and pouring into the inner diameter
Outer diameter
Diameter of pressure head
In the stainless steel mold, cold press molding is carried out under 20MPa to obtain a blank body with the thickness of 1-2 mm.
5) Mixing the above 0.10% G/Bi0.5Sb1.5Te3And placing the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment. The heat treatment process parameters are as follows: the heat treatment temperature is 400 ℃, the heat treatment time is 2 hours, and the heating rate is 2-10 ℃/min.
0.10% G/Bi obtained by the above heat treatment0.5Sb1.5Te3The XRD spectrum of the composite material is shown in FIG. 1 as 0.10% G/Bi0.5Sb1.5Te3The spectral lines show that the relation curves of the electrical conductivity, the Seebeck coefficient, the thermal conductivity and the ZT value of the material under 300-480K and the temperature are shown as 0.10 percent G/Bi in the graphs 3-60.5Sb1.5Te3The curves show: at 310K, the power factor is 1.32 mW.m-1K, thermal conductivity as low as 0.45 W.m-1·K-1Finally, the integrated thermoelectric figure of merit ZT reaches a maximum of 0.90.
Example 3: 0.15% G/Bi0.5Sb1.5Te3Composite thermoelectric material
Preparation of 0.15% G/Bi in the present invention0.5Sb1.5Te3The raw material selection and the specific operation flow of the composite thermoelectric material are as follows:
bi is prepared by adopting a melting annealing and quenching method0.5Sb1.5Te3Casting of base materialA block; the preparation method comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the use amounts of high-purity metals Bi (99.99 percent, powder), Sb (99.99 percent, powder) and Te (99.99 percent, powder), sealing the high-purity metals Bi (99.99 percent, powder) into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing for 10 hours at 800 ℃, quenching the melt to obtain a target product Bi0.5Sb1.5Te3The casting block is a base material;
1) and crushing and ball-milling the cast block to obtain matrix powder with the particle size of 1-5 microns. The ball milling process parameters are as follows: the ball milling speed is 200r/min, and the ball milling time is 4 h.
2) Grinding industrial grade graphite block, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as 0.15% G/Bi0.5Sb1.5Te3The second phase graphite raw material in the composite thermoelectric material.
3) According to the chemical composition 0.15% G/Bi0.5Sb1.5Te3Calculating and weighing 3G of matrix powder and corresponding graphite powder, ultrasonically dispersing the graphite powder in 20ml of absolute ethyl alcohol, adding the matrix powder, ultrasonically dispersing for 15min, centrifuging for 5min at the rotating speed of 800r/min, taking lower-layer slurry, and vacuum drying for 1h at the temperature of 60 ℃ to obtain 0.15% G/Bi0.5Sb1.5Te3Composite thermoelectric powder.
4) Weighing the above 0.15% G/Bi0.5Sb1.5Te31-2 g of composite thermoelectric powder, and pouring into the inner diameter
Outer diameter
Diameter of pressure head
In the stainless steel mold, cold press molding is carried out under 20MPa to obtain a blank body with the thickness of 1-2 mm.
5) Mixing the above 0.15% G/Bi0.5Sb1.5Te3And placing the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment. The heat treatment process parameters are as follows: temperature of heat treatmentThe temperature is 400 ℃, the heat treatment time is 2 hours, and the heating rate is 2-10 ℃/min.
0.15% G/Bi obtained by the above heat treatment0.5Sb1.5Te3The XRD spectrum of the composite material is shown in FIG. 1 as 0.15% G/Bi0.5Sb1.5Te3The spectral lines show that the relation curves of the electrical conductivity, the Seebeck coefficient, the thermal conductivity and the ZT value of the material under 300-480K and the temperature are shown as 0.15 percent G/Bi in the graphs 3-60.5Sb1.5Te3The curves show: at 310K, the power factor is 1.19 mW.m-1K, thermal conductivity as low as 0.41 W.m-1·K-1Finally, the integrated thermoelectric figure of merit ZT reaches a maximum of 0.89.
Example 4: 0.20% G/Bi0.5Sb1.5Te3Composite thermoelectric material
Preparation of 0.20% G/Bi in the present invention0.5Sb1.5Te3The raw material selection and the specific operation flow of the composite thermoelectric material are as follows:
bi is prepared by adopting a melting annealing and quenching method0.5Sb1.5Te3An ingot of a base material; the preparation method comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the use amounts of high-purity metals Bi (99.99 percent, powder), Sb (99.99 percent, powder) and Te (99.99 percent, powder), sealing the high-purity metals Bi (99.99 percent, powder) into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing for 10 hours at 800 ℃, quenching the melt to obtain a target product Bi0.5Sb1.5Te3The casting block is a base material;
1) and crushing and ball-milling the cast block to obtain matrix powder with the particle size of 1-5 microns. The ball milling process parameters are as follows: the ball milling speed is 200r/min, and the ball milling time is 4 h.
2) Grinding industrial grade graphite block, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as 0.20% G/Bi0.5Sb1.5Te3The second phase graphite raw material in the composite thermoelectric material.
3) According to the chemical composition 0.20% G/Bi0.5Sb1.5Te3Calculating and weighing 3g of matrix powder and corresponding graphite powder, and ultrasonically treating the graphite powderDispersing in 20ml anhydrous ethanol, adding matrix powder, ultrasonically dispersing for 15min, centrifuging at rotation speed of 800r/min for 5min, taking lower layer slurry, and vacuum drying at 60 deg.C for 1h to obtain 0.20% G/Bi0.5Sb1.5Te3Composite thermoelectric powder.
4) Weighing the above 0.20% G/Bi0.5Sb1.5Te31-2 g of composite thermoelectric powder, and pouring into the inner diameter
Outer diameter
Diameter of pressure head
In the stainless steel mold, cold press molding is carried out under 20MPa to obtain a blank body with the thickness of 1-2 mm.
5) Mixing the above 0.20% G/Bi0.5Sb1.5Te3And placing the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment. The heat treatment process parameters are as follows: the heat treatment temperature is 400 ℃, the heat treatment time is 2 hours, and the heating rate is 2-10 ℃/min.
0.20% G/Bi obtained by the above heat treatment0.5Sb1.5Te3The XRD spectrum of the composite material is shown in FIG. 1 as 0.20% G/Bi0.5Sb1.5Te3The spectral lines show that the relation curves of the electrical conductivity, the Seebeck coefficient, the thermal conductivity and the ZT value of the material under 300-480K and the temperature are shown as 0.20 percent G/Bi in the graphs 3-60.5Sb1.5Te3The curves show: at 320K, the power factor is 1.06 mW.m-1K, thermal conductivity as low as 0.40 W.m-1·K-1Finally, the integrated thermoelectric figure of merit ZT reached a maximum of 0.81.
Comparative example 1: bi0.5Sb1.5Te3Matrix thermoelectric material
Preparation of Bi in the invention0.5Sb1.5Te3The specific operation flow of the matrix thermoelectric material is as follows:
bi is prepared by adopting a melting annealing and quenching method0.5Sb1.5Te3An ingot of a base material; the preparation method comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the use amounts of high-purity metals Bi (99.99 percent, powder), Sb (99.99 percent, powder) and Te (99.99 percent, powder), sealing the high-purity metals Bi (99.99 percent, powder) into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing for 10 hours at 800 ℃, quenching the melt to obtain a target product Bi0.5Sb1.5Te3The casting block is a base material;
1) and crushing and ball-milling the cast block to obtain matrix powder with the particle size of 1-5 microns. The ball milling process parameters are as follows: the ball milling speed is 200r/min, and the ball milling time is 4 h.
2) Weighing 3g of matrix powder, adding the matrix powder into 20ml of absolute ethyl alcohol, performing ultrasonic dispersion for 15min, centrifuging for 5min at the rotating speed of 800r/min, taking the lower-layer slurry, and performing vacuum drying for 1h at 60 ℃ to obtain Bi0.5Sb1.5Te3Thermoelectric powder.
3) Weighing the Bi0.5Sb1.5Te31-2 g of thermoelectric powder, and pouring into the inner diameter
Outer diameter
Diameter of pressure head
In the stainless steel die, cold pressing and molding are carried out under 20MPa, and a blank body with the thickness of 1-2 mm is obtained.
4) Mixing the above Bi0.5Sb1.5Te3And putting the material blank into a hydrogen atmosphere sintering furnace for heat treatment. The heat treatment process parameters are as follows: the heat treatment temperature is 400 ℃, the heat treatment time is 2 hours, and the heating rate is 2-10 ℃/min.
Bi obtained after the heat treatment0.5Sb1.5Te3XRD spectrum of thermoelectric material is shown in Bi in figure 10.5Sb1.5Te3The spectral lines show that the relation curves of the electrical conductivity, the Seebeck coefficient, the thermal conductivity and the ZT value of the material under 300-480K and the temperature are shown as Bi in figures 3-60.5Sb1.5Te3The curves show: at 320K, the power factor is 1.40 mW.m-1K, thermal conductivity of 0.60 W.m-1·K-1Finally, the integrated thermoelectric figure of merit ZT reaches a maximum value of 0.74. As a result of comparative examples 1 to 4, it was found that: the ZT value of the composite material is higher than that of the base material, which shows that the thermoelectric property of the material can be effectively regulated and controlled by adding a trace amount of the second phase G, and further the thermoelectric property of the material is improved. And the sample with the optimal ZT value is that the addition amount of G is 0.05%, and the maximum ZT value of the sample at 320K is 1.05 which is improved by 42% compared with the base material.
Comparative example 2: bi0.5Sb1.5Te3Matrix and graphene composite thermoelectric material
Taking graphene as a second phase, comparing the second phase with a paper of 'preparation and performance research of graphene composite bismuth telluride-based thermoelectric material' by author of Tonghua university as Libeibei, in which Bi is used0.5Sb1.5Te3The composite thermoelectric material is prepared by SPS (spark plasma sintering) process. Although the thermoelectric performance of graphite G is far inferior to that of graphene, G/Bi0.5Sb1.5Te3The thermoelectric property of the composite is superior to that of graphene/Bi0.5Sb1.5Te3The composite thermoelectric material, the relevant performance versus ratio, is shown in table 1 below. The composite thermoelectric material can be used as a raw material for preparing and assembling a high-performance flexible thermoelectric device, and is expected to realize breakthrough in the commercial application of the flexible thermoelectric device.
TABLE 1G/Bi0.5Sb1.5Te3And graphene/Bi0.5Sb1.5Te3Thermoelectric Performance comparison of composite thermoelectric materials
Claims (10)
1. Bismuth telluride based composite thermoelectric material applied to flexible thermoelectric deviceCharacterized in that the composition of the thermoelectric material is x G/Bi0.5Sb1.5Te3G is graphite, wherein x is second-phase graphite in matrix Bi0.5Sb1.5Te3The mass percentage of x is more than 0 and less than or equal to 0.20 percent, and the graphite is obtained by grinding an industrial grade graphite block into powder and sieving the powder with a 400-mesh sieve to obtain graphite powder with the particle size of less than 37 mu m.
2. The bismuth telluride-based composite thermoelectric material for flexible thermoelectric device applications as claimed in claim 1, wherein x is 0.05%.
3. The preparation method of the bismuth telluride-based composite thermoelectric material applied to the flexible thermoelectric device according to claim 1, wherein the preparation method comprises the following steps:
1) preparing Bi by adopting a melting annealing and quenching method0.5Sb1.5Te3Ingot of a base material, preparing Bi0.5Sb1.5Te3Crushing and ball-milling a base material ingot to obtain powder with the particle size of 1-5 mu m;
2) grinding industrial grade graphite block into powder, sieving with 400 mesh sieve to obtain graphite powder with particle size less than 37 μm as xG/Bi0.5Sb1.5Te3A second phase in the composite thermoelectric material;
3) calculating and weighing matrix powder and corresponding graphite powder according to chemical composition, ultrasonically compounding in absolute ethyl alcohol at normal temperature and normal pressure for 10-20 min, centrifuging, and vacuum drying to obtain x G/Bi0.5Sb1.5Te3The composite thermoelectric powder of (3);
4) x G/Bi0.5Sb1.5Te3Pouring the composite thermoelectric powder into a stainless steel mold, and performing cold pressing to obtain a composite material blank with the thickness of 1-2 mm;
5) and putting the composite material blank into a hydrogen atmosphere sintering furnace for heat treatment to obtain the bismuth telluride based composite thermoelectric material.
4. Use of a flexible thermoelectric device according to claim 3The preparation method of the bismuth telluride-based composite thermoelectric material is characterized in that Bi in the step 1)0.5Sb1.5Te3The preparation method of the base material ingot comprises the following steps: has a nominal composition of Bi0.5Sb1.5Te3Weighing the amounts of high-purity metal Bi powder, Sb powder and Te powder, sealing the high-purity metal Bi powder, Sb powder and Te powder into a quartz tube in a vacuum state, placing the quartz tube into a melting furnace, performing melt annealing at the temperature of 700-0.5Sb1.5Te3And (5) casting.
5. The method for preparing the bismuth telluride-based composite thermoelectric material applied to the flexible thermoelectric device according to claim 3, wherein the ball milling process parameters in the step 1) are as follows: the ball milling speed is 200-300 r/min, and the ball milling time is 3-5 h.
6. The method for preparing the bismuth telluride-based composite thermoelectric material applied to the flexible thermoelectric device according to claim 3, wherein the centrifugal process parameters in the step 3) are as follows: the centrifugal speed is 600-1000 r/min, and the centrifugal time is 5-10 min.
7. The method for preparing the bismuth telluride-based composite thermoelectric material applied to the flexible thermoelectric device as claimed in claim 3, wherein the vacuum drying process parameters in the step 3) are as follows: the drying temperature is 40-60 ℃, and the drying time is 1-2 h.
8. The method for preparing the bismuth telluride-based composite thermoelectric material for the flexible thermoelectric device as claimed in claim 3, wherein the stainless steel mold in the step 4) has an inner diameter
Outer diameter
Diameter of pressure head
9. The method for preparing the bismuth telluride-based composite thermoelectric material for the flexible thermoelectric device as claimed in claim 3, wherein the pressing process parameters in the step 4) are as follows: the pressing pressure is 10-20 MPa.
10. The method for preparing the bismuth telluride-based composite thermoelectric material for the flexible thermoelectric device as claimed in claim 3, wherein the heat treatment parameters in the step 5) are as follows: the heat treatment temperature is 350-450 ℃, the heat treatment time is 1.5-2.5 h, and the heating rate is 2-10 ℃/min.
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| CN110767796B (en) * | 2019-10-14 | 2021-06-01 | 东华大学 | Two-dimensional transition metal carbide/bismuth telluride or derivative thereof based thermoelectric composite material and preparation thereof |
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| CN112234137B (en) * | 2020-10-30 | 2023-05-02 | 武汉理工大学 | Large-area flexible thermoelectric refrigeration thin film cascade device and preparation method thereof |
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| CN113206185B (en) * | 2021-05-18 | 2022-06-17 | 四川大学 | Preparation method of p-type bismuth telluride-based composite thermoelectric material |
| CN114210978A (en) * | 2021-12-22 | 2022-03-22 | 中国电子科技集团公司第十八研究所 | Hot extrusion molding method of bismuth telluride thermoelectric material |
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