CN110098313A - A kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material - Google Patents
A kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material Download PDFInfo
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- CN110098313A CN110098313A CN201910325213.4A CN201910325213A CN110098313A CN 110098313 A CN110098313 A CN 110098313A CN 201910325213 A CN201910325213 A CN 201910325213A CN 110098313 A CN110098313 A CN 110098313A
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- bismuth telluride
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001125 extrusion Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 13
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000004615 ingredient Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000005619 thermoelectricity Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
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- 238000003825 pressing Methods 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 238000004857 zone melting Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000002114 nanocomposite Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
- H10N15/10—Thermoelectric devices using thermal change of the dielectric constant, e.g. working above and below the Curie point
- H10N15/15—Thermoelectric active materials
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Abstract
The present invention provides a kind of preparation methods of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material, comprising the following steps: using Bi, Sb and Te elemental powders as raw material, by BixSb2‑xTe3Stoichiometric ratio weighs ingredient, above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe vacuumizes sealing, the quartz glass tube of sealing or high-boron-silicon glass pipe are put into rocking furnace again and carry out abundant melting, after melting terminates, rocking furnace burner hearth is rotated to vertical position, p-type bismuth telluride based alloys crystal bar is made after cooling；P-type bismuth telluride based alloys crystal bar obtained is cut into block, by block be fitted into equal channel angular extrusion die be placed in hot-pressed sintering furnace be sintered extruding to get preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material.P-type bismuth telluride-base polycrystalline bulk thermoelectric material resistivity is lower prepared by the present invention, Seebeck coefficient is higher, thermal conductivity is low, can obtain maximum ZT value 1.55 in 343K.
Description
Technical field
The invention belongs to bismuth telluride-base thermoelectric material technical fields, and in particular to a kind of preferred orientation p-type bismuth telluride-base is more
Brilliant block thermoelectric material and preparation method thereof.
Background technique
The Bi of zone melting method production2Te3Based alloy has a preferable thermoelectricity capability, ZT value at room temperature 1 or so,
It has been widely used in thermoelectricity industry.But in the Bi of zone melting method production2Te3In based alloy, Te (1)-Te (1) atomic layer
Between only rely on Van der Waals force and be combined together, machining property is poor.Bi is melted in order to solve area2Te3Based alloy machining
The problem of performance difference, many scientific research institutions and production firm prepare polycrystalline Bi using PM technique2Te3Base thermoelectricity material.Its
The research of middle p-type makes great progress.Ren et al. introduces nanoparticle, system by high-energy ball milling and direct current heat pressing process
For p-type Bi2-xSbxTe3Nanocomposite considerably reduces lattice thermal conductivity, and obtained ZT value is up to 1.3 and 1.4.It removes
Except this, some scholars introduce hetero-junctions by nano combined or structure regulating means and generate energy filtering effect, mention simultaneously
High Seebeck coefficient and conductivity, to promote ZT value.Li et al. people is received by being mixed into the SiC of 0.4vol.% in BiSbTe matrix
Rice grain in conjunction with high-energy ball milling and discharge plasma sintering process, while improving Seebeck coefficient and conductivity, reduces heat
Conductance finally achieves maximum ZT value 1.33 in 373K；Zu et al. passes through to Bi0.5Sb1.5Te3It carries out liquid processing and combines melting
Spinning, ball milling and discharge plasma sintering process construct a large amount of 60 ° of twin boundaries to scatter low energy carrier, improve Seebeck
Coefficient and carrier mobility reduce lattice thermal conductivity, maximum ZT value are finally promoted to 1.42 by 1.12 in 348K.
But while applied powder metallurgy technique preparation p-type bismuth telluride-base thermoelectric material reduction lattice thermal conductivity, due to
The nanocrystal of a large amount of crystal boundaries and random orientation is introduced, material internal carrier mobility can also significantly reduce, and lead to material
Resistivity inevitably increases, and ZT value is promoted limited.And during conventional powder processed, it is oxidizable also to expose material,
The problems such as being easily introduced oxide impurity.
Summary of the invention
The present invention is directed to overcome prior art defect, and it is an object of the present invention to provide a kind of crystal grain refinement is abundant, preferred orientation is good, work
The preparation method of simple, high production efficiency the preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material of skill, prepared p-type
Bismuth telluride-base polycrystalline bulk thermoelectric material resistivity is lower, Seebeck coefficient is higher, thermal conductivity is low, can finally obtain in 343K
Maximum ZT value is 1.55.
To realize above-mentioned purpose, the technical solution adopted by the present invention are as follows:
A kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material, comprising the following steps:
(1) using Bi, Sb and Te elemental powders as raw material, by BixSb2-xTe3Stoichiometric ratio weighs ingredient, and 0.3≤x≤
0.5；
(2) above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe and vacuumize sealing, then by the quartzy glass of sealing
Glass pipe or high-boron-silicon glass pipe, which are put into rocking furnace, carries out abundant melting, and after melting terminates, rocking furnace burner hearth is rotated to perpendicular
P-type bismuth telluride based alloys crystal bar is made after cooling in straight position；
(3) p-type bismuth telluride based alloys crystal bar obtained in step (2) is cut into block, the channels such as block loading is turned
Angle extrusion die, which is placed in hot-pressed sintering furnace, is sintered extruding to get preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectricity
Material.
It is raw material that Bi, Sb and Te elemental powders of the mass percentage greater than 99.99% are chosen in step (1).
High melt is carried out in 590~750 DEG C of temperature in step (2), smelting time is 5~120min.
Equal channel angular extrusion die described in step (3) includes pressure head, formed punch, flapper, right angle fixture and mould
Has ontology, wherein die ontology is in cube-shaped with chamfering, and right angle fixture is located at the bottom of die ontology, flapper position
In the side of die ontology, die ontology is fixed jointly with flapper for right angle fixture, the top of the formed punch and pressure
Head connection, the bottom of formed punch be located in the channel of die ontology and under the action of pressure head to the block in die ontology into
Row squeezes.
Sintering described in step (3) squeezes specific steps are as follows:
(3-1) does not apply pressure first, and furnace body is warming up to 300~510 DEG C, keeps the temperature 30min；
(3-2) then applies the principal pressure of 50~200MPa and the back pressure of 10~100MPa, with squeezing for 5~10mm/min
Pressure speed squeezes block；
(3-3) is every squeezed a time after, by equal channel angular extrusion die be rotated in a clockwise direction 90 ° again with
Identical technological parameter is squeezed in (3-2), is amounted to and is squeezed 4 times；
(3-4) entire extrusion process is completed in air or vacuum or inert atmosphere, and is protected with 300~510 DEG C always
Temperature is until squeezing terminates.
High melt prepares p-type bismuth telluride based alloys crystal bar first in the present invention, and then Equal-channel Angular Pressing preparation is selected
Excellent orientation p-type bismuth telluride-base polycrystalline thermoelectric material, compared with prior art, the invention has the following advantages:
1, using Bi, Sb and Te elemental powders or particle as raw material, 590 DEG C of melting 5min can be obtained single-phase the present invention
BixSb2-xTe3(0.3≤x≤0.5) crystal bar；Then extrusion forming directly is carried out to the crystal bar that melting obtains, eliminates powder mistake processed
The pollution and oxidation of journey, more suitable for large-scale production；Four-pass squeeze total time it is most short only need 20min, i.e., in the short period
Interior that preferred orientation p-type bismuth telluride-base polycrystalline thermoelectric material can quickly be made, relative density is more than 99%, has simple process, life
Produce the feature that the period is short, high production efficiency, product consistency are high.2, the present invention is obviously advantageous using Equal Channel Angular Pressing
In the abundant refinement of crystal grain and preferred orientation.3, since crystal grain is uniformly refined to same size, the property of made thermoelectric material
It can stablize, favorable repeatability, can obtain maximum ZT value in 343K is 1.55.
In conclusion the present invention has the characteristics that simple production process, with short production cycle and high production efficiency, it is prepared
Preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material product purity is higher, consistency is high, grain refining effect is good, crystal grain
Preferred orientation is strong, and conductivity is high, dimensionless thermoelectric figure of merit is high.
Detailed description of the invention
Fig. 1 is the preferred orientation factor graph of p-type bismuth telluride-base polycrystalline bulk thermoelectric material prepared by the present invention；
Fig. 2 is the SEM figure of p-type bismuth telluride-base polycrystalline bulk thermoelectric material fracture prepared by the present invention；
Fig. 3 is p-type Bi prepared by the present invention0.5Sb1.5Te3The resistivity of polycrystalline bulk thermoelectric material difference measurement direction with
The curve graph of temperature change；
Fig. 4 is p-type Bi prepared by the present invention0.5Sb1.5Te3The Seebeck system of polycrystalline bulk thermoelectric material difference measurement direction
The curve graph that number varies with temperature；
Fig. 5 is p-type Bi prepared by the present invention0.5Sb1.5Te3The thermal conductivity of polycrystalline bulk thermoelectric material difference measurement direction with
The curve graph of temperature change；
Fig. 6 is p-type Bi prepared by the present invention0.5Sb1.5Te3The ZT value of polycrystalline bulk thermoelectric material difference measurement direction is with temperature
Spend the curve graph of variation；
Fig. 7 is the equal channel angular extrusion die schematic diagram that the present invention designs.
Specific embodiment
Detailed specific description done to the present invention combined with specific embodiments below, but protection scope of the present invention not office
It is limited to following embodiment.
The structure of equal channel angular extrusion die employed in following embodiment is as shown in fig. 7, the equal channel angular
Extrusion die includes pressure head 1, formed punch 2, flapper 3, right angle fixture 4 and die ontology 6, and wherein die ontology 6 is in and has
Chamfering it is cube-shaped, right angle fixture 4 is located at the bottom of die ontology 6, and flapper 3 is located at the side of die ontology, right angle
Die ontology 6 is fixed jointly with flapper 3 for fixture 4, and the top of the formed punch is connect with pressure head, the bottom position of formed punch
It is squeezed in the channel of die ontology and to the block 5 being located in die ontology under the action of pressure head.
Embodiment 1
Preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material provided in the present embodiment the preparation method is as follows:
Bi, Sb and Te elemental powders using mass percentage greater than 99.99% is raw materials, by Bi0.5Sb1.5Te3Chemistry
Ingredient is compared in metering；
Above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe and vacuumize sealing, then by the quartz glass tube of sealing
Or high-boron-silicon glass pipe is put into rocking furnace, carries out high melt, smelting temperature is 710 DEG C, smelting time 5min.Melting knot
After beam, rocking furnace burner hearth is rotated to plumb position, Slow cooling, high density p-type bismuth telluride based alloys crystal bar is made；
P-type bismuth telluride based alloys crystal bar obtained is cut into block, after block is packed into equal channel angular extrusion die
It is placed in hot-pressed sintering furnace and is squeezed, extrusion process are as follows:
(1) do not apply pressure first, furnace body is warming up to 350 DEG C, keeps the temperature 30min；
(2) apply the principal pressure of 50~200MPa and the back pressure of 10~100MPa, then with the extrusion speed of 5mm/min
Block is squeezed；
(3) it is every squeezed a time after, by mold be rotated in a clockwise direction 90 ° again with technique identical in (2) ginseng
Number is squeezed, and is so repeated 4 times；
(4) entire extrusion process is completed in air or vacuum or inert atmosphere, and always with 350 DEG C of heat preservations until squeezing
Pressure terminates.
Up to preferred orientation p-type Bi after extruding0.5Sb1.5Te3Polycrystalline bulk thermoelectric material.To made in the present embodiment
Material detected, the preferred orientation factor as shown in Figure 1, from figure 1 it appears that with squeeze passage increase,
Orientation factor steps up.The SEM cross-section diagram of Fracture Profile in Metallic Materials squeezes as shown in Fig. 2, as can be seen from Figure 2 passing through four-pass,
Material internal crystallite dimension is refined to micron order by the grade before squeezing, and obedience is uniformly distributed, and the preferred orientation of crystal grain is non-
Chang Mingxian.
The thermoelectricity capability of above-mentioned material as seen in figures 3-6, as can be seen from the figure due to excellent preferable grain orientation, carries
Stream transport factor be substantially improved, be greatly reduced along the direction of extrusion resistivity of material, and Seebeck coefficient can maintain compared with
High level, final made p-type bismuth telluride-base polycrystalline bulk thermoelectric material maximum ZT value is up to 1.55, conventional powders more in the market
Metallurgical product and traditional zone melting single-crystal product improve 55%.
Embodiment 2
Preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material provided in the present embodiment the preparation method is as follows:
Bi, Sb and Te elemental powders using mass percentage greater than 99.99% is raw materials, by Bi0.45Sb1.55Te3Chemistry
Ingredient is compared in metering；
Above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe and vacuumize sealing, then by the quartz glass tube of sealing
Or high-boron-silicon glass pipe is put into rocking furnace, carries out high melt, smelting temperature is 680 DEG C, smelting time 10min.Melting
After end, rocking furnace burner hearth is rotated to plumb position, Slow cooling, high density p-type bismuth telluride based alloys crystal bar is made；
P-type bismuth telluride based alloys crystal bar obtained is cut into block, after block is packed into equal channel angular extrusion die
It is placed in hot-pressed sintering furnace and is squeezed, extrusion process are as follows:
(1) do not apply pressure first, furnace body is warming up to 400 DEG C, keeps the temperature 30min；
(2) apply the principal pressure of 50~200MPa and the back pressure of 10~100MPa, then with the extrusion speed of 6mm/min
Block is squeezed；
(3) it is every squeezed a time after, by mold be rotated in a clockwise direction 90 ° again with technique identical in (2) ginseng
Number is squeezed, and is so repeated 4 times；
(4) entire extrusion process is completed in air or vacuum or inert atmosphere, and always with 400 DEG C of heat preservations until squeezing
Pressure terminates.
Up to preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material after extruding.
Embodiment 3
Preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material provided in the present embodiment the preparation method is as follows:
Bi, Sb and Te elemental powders using mass percentage greater than 99.99% is raw materials, by Bi0.4Sb1.6Te3Chemistry
Ingredient is compared in metering；
Above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe and vacuumize sealing, then by the quartz glass tube of sealing
Or high-boron-silicon glass pipe is put into rocking furnace, carries out high melt, smelting temperature is 650 DEG C, smelting time 15min.Melting
After end, rocking furnace burner hearth is rotated to plumb position, Slow cooling, high density p-type bismuth telluride based alloys crystal bar is made；
By p-type bismuth telluride based alloys crystal bar obtained be cut into having a size of block, by block loading equal channel angular squeeze
Compression mould is placed in hot-pressed sintering furnace and is squeezed, extrusion process are as follows:
(1) do not apply pressure first, furnace body is warming up to 450 DEG C, keeps the temperature 30min；
(2) apply the principal pressure of 50~200MPa and the back pressure of 10~100MPa, then with the extruding speed of 10mm/min
Degree squeezes block；
(3) it is every squeezed a time after, by mold be rotated in a clockwise direction 90 ° again with technique identical in (2) ginseng
Number is squeezed, and is so repeated 4 times；
(4) entire extrusion process is completed in air or vacuum or inert atmosphere, and always with 450 DEG C of heat preservations until squeezing
Pressure terminates.
Up to preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material after extruding.
Claims (5)
1. a kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material, it is characterised in that including following step
It is rapid:
(1) using Bi, Sb and Te elemental powders as raw material, by BixSb2-xTe3Stoichiometric ratio weighs ingredient, 0.3≤x≤0.5；
(2) above-mentioned raw materials are packed into quartz glass tube or high-boron-silicon glass pipe and vacuumize sealing, then by the quartz glass tube of sealing
Or high-boron-silicon glass pipe is put into rocking furnace and carries out abundant melting, and after melting terminates, rocking furnace burner hearth is rotated to vertical position
It sets, p-type bismuth telluride based alloys crystal bar is made after cooling；
(3) p-type bismuth telluride based alloys crystal bar obtained in step (2) is cut into block, block loading equal channel angular is squeezed
Compression mould, which is placed in hot-pressed sintering furnace, is sintered extruding to get preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material.
2. a kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material according to claim 1,
Be characterized in that: it is raw material that Bi, Sb and Te elemental powders of the mass percentage greater than 99.99% are chosen in step (1).
3. a kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material according to claim 1,
It is characterized in that: carrying out high melt in 590~750 DEG C of temperature in step (2), smelting time is 5~120min.
4. a kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material according to claim 1,
Be characterized in that: equal channel angular extrusion die described in step (3) includes pressure head, formed punch, flapper, right angle fixture and mould
Has ontology, wherein die ontology is in cube-shaped with chamfering, and right angle fixture is located at the bottom of die ontology, flapper position
In the side of die ontology, die ontology is fixed jointly with flapper for right angle fixture, the top of the formed punch and pressure
Head connection, the bottom of formed punch be located in the channel of die ontology and under the action of pressure head to the block in die ontology into
Row squeezes.
5. a kind of preparation method of preferred orientation p-type bismuth telluride-base polycrystalline bulk thermoelectric material according to claim 4,
Be characterized in that: sintering described in step (3) squeezes specific steps are as follows:
(3-1) does not apply pressure first, and furnace body is warming up to 300~510 DEG C, keeps the temperature 30min；
(3-2) then applies the principal pressure of 50~200MPa and the back pressure of 10~100MPa, with the extruding speed of 5~10mm/min
Degree squeezes block；
(3-3) is every squeezed a time after, equal channel angular extrusion die is rotated in a clockwise direction 90 ° again with (3-2)
In identical technological parameter squeezed, amount to squeeze 4 times；
(3-4) entire extrusion process is completed in air or vacuum or inert atmosphere, and straight with 300~510 DEG C of heat preservations always
Terminate to extruding.
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Cited By (10)
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| CN112079638A (en) * | 2020-09-22 | 2020-12-15 | 哈尔滨工业大学 | P-type bismuth telluride-based thermoelectric material with high thermoelectric and mechanical properties and preparation method thereof |
| CN112500164A (en) * | 2020-12-14 | 2021-03-16 | 深圳先进电子材料国际创新研究院 | Bismuth telluride thermoelectric material and preparation method thereof |
| CN112694070A (en) * | 2019-10-23 | 2021-04-23 | 中国科学院宁波材料技术与工程研究所 | Composite thermoelectric material and preparation method thereof |
| CN112864300A (en) * | 2019-11-28 | 2021-05-28 | 中国科学院大连化学物理研究所 | Bismuth telluride-based alloy thin film-perovskite type oxide heterojunction composite thermoelectric material and preparation and application thereof |
| CN113023687A (en) * | 2021-03-04 | 2021-06-25 | 南昌工程学院 | Method for preparing nano bismuth antimony tellurium based on spark plasma sintering technology |
| CN113161474A (en) * | 2021-05-06 | 2021-07-23 | 先导薄膜材料（广东）有限公司 | P-type bismuth telluride-based alloy material and preparation method thereof |
| CN113328031A (en) * | 2020-09-01 | 2021-08-31 | 中国科学院宁波材料技术与工程研究所 | High-strength and high-efficiency bismuth telluride block and preparation method and application thereof |
| CN113421959A (en) * | 2021-06-22 | 2021-09-21 | 深圳大学 | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof |
| CN113735582A (en) * | 2021-09-09 | 2021-12-03 | 武汉科技大学 | Preparation method of bismuth telluride-based thermoelectric material |
| CN115558997A (en) * | 2022-09-20 | 2023-01-03 | 杭州大和热磁电子有限公司 | Preparation method for improving mechanical properties of bismuth telluride-based thermoelectric material |
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