CN107316935B - The preparation method of tellurium bismuthino thermoelectric material - Google Patents
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- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910052714 tellurium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000007731 hot pressing Methods 0.000 claims abstract description 65
- 239000000956 alloy Substances 0.000 claims abstract description 55
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 55
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- 230000005619 thermoelectricity Effects 0.000 claims description 6
- 238000003723 Smelting Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000000047 product Substances 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- -1 bismuthino Chemical group 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 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
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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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
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of preparation methods of tellurium bismuthino thermoelectric material, and the preparation method is first by p-type Bi x Sb 2‑x Te 3‑y Se y Alloy pig carries out a hot pressing, forms an alloy block, wherein 0.4≤x≤ 0.52,0≤y≤0.15；An alloy block is overturn into 90 ° of placements by axis of its length direction again, secondary hot pressing is carried out, obtains tellurium bismuthino thermoelectric material.The present invention obtains qualified tellurium bismuthino thermoelectric material by the way that the alloy pig after melting is directly carried out hot pressing twice.Preparation method of the present invention is simple, high production efficiency, and the electric property and mechanical performance of obtained product significantly improve.
Description
Technical field
The present invention relates to thermoelectric material fields, more particularly, to a kind of preparation method of tellurium bismuthino thermoelectric material.
Background technique
The tellurium bismuthino solid solution alloy thermoelectric material best as near room temperature performance, in thermo-electric generation and semiconductor refrigerating
Field is using very extensive.
Currently, production tellurium bismuthino thermoelectric material is mainly two kinds, one is zone refining, another kind is to be crushed powder hot pressing processed
Processing.First method is that the alloy pig obtained after melting is prepared into orientation polycrystalline or monocrystal rod using zone refining technique.
The series of advantages such as this method has cost of investment low, easy large-scale production, and product thermoelectricity capability is excellent.Though zone refining technique
So have above-mentioned advantage, but disadvantage is equally obvious: the one side production cycle is longer, melts stick growth rate, crystal bar for strict control area
Production generally require after ten a few houres, the unqualified part of caput tail performance needs cutting process, causes waste of material；It is another
The machining property of aspect zone refining production sample is poor, high rejection rate during following process.Second method be by
The alloy pig of melting or area melt stick and carry out after being crushed powder processed, then use hot-pressing processing.This method can not damage original heat
On the basis of electrical property, the mechanical performance of product is improved.But this method is crushed powder in pulverizing process and easily aoxidizes and introduce
The fine dusts of impurity, generation are harmful to the human body, and pressing process is stringent, at high cost, and process flow is long, and production efficiency is low.
Product mechanical performance can directly be improved by seeking one kind, while maintain the simple process of the excellent thermoelectricity capability of product to be
Popular research direction.Molten alloy ingot is generally as intermediate products by the either broken powder hot pressing processed of subsequent sections melting
Reason, it is with Bi that Chinese invention patent CN200810038766.3, which discloses a kind of preparation method of bismuth telluride based sintered fuel,2Te3
It is starting material that stick is melted in base area, removes oxide on surface by sandblasting, precompressed carries out discharge plasma sintering under vacuum conditions
Crystal bar material obtains agglomerated material.Chinese invention patent CN201410157880.3 discloses a kind of high property using cold forming
Can thermoelectric material manufacturing method: after pyroelectric ingot casting, carry out carrying out it under anaerobic up to 400MPa ~
2000MPa cold forming, heat treatment manufacture thermoelectric material.Chinese invention patent CN201410562489.1 discloses a kind of raising N
The processing method of the powder sintered block thermoelectric material performance of type bismuth telluride-base: being that hot-forming bismuth telluride based bulk is placed in mould
In tool, the change rate low speed thermal deformation along short transverse is controlled under 500 ~ 550 DEG C, pressure condition.The above-mentioned prior art
Stick is often melted as raw material using hot pressing block either area, pressing process need to be through stringent control, and preparation cost is high, process flow
It is long.
Accordingly, it is desirable to provide a kind of preparation method of new tellurium bismuthino thermoelectric material.
Summary of the invention
In view of this, the present invention provides a kind of simple processes, tellurium bismuthino thermoelectric material at low cost, good product performance
Preparation method.
To achieve the goals above, technical solution of the present invention: a kind of preparation method of tellurium bismuthino thermoelectric material, first by p
Type Bi x Sb 2-x Te 3-y Se y Alloy pig carries out a hot pressing, forms an alloy block, wherein 0.4≤x≤ 0.52,0≤y≤0.15；
An alloy block is overturn into 90 ° of placements by axis of its length direction again, secondary hot pressing is carried out, obtains tellurium bismuthino thermoelectric material.
As a further improvement of the present invention, the temperature of a hot pressing is 250 ~ 350 DEG C, pressure is 5 ~ 30MPa.
As a further improvement of the present invention, the heating rate of a hot pressing is 5 ~ 10 DEG C/min.
As a further improvement of the present invention, the time of a hot pressing is 50 ~ 60min.
As a further improvement of the present invention, the temperature of the secondary hot pressing is 350 ~ 450 DEG C, pressure is 15 ~ 45MPa.
As a further improvement of the present invention, the heating rate of the secondary hot pressing is 10 ~ 20 DEG C/min.
As a further improvement of the present invention, the time of the secondary hot pressing is 5 ~ 60min.
As a further improvement of the present invention, two ends of an alloy block length direction need to cut off 0.5 respectively ~
3mm。
As a further improvement of the present invention, the p-type Bi x Sb 2-x Te 3-y Se y Alloy pig be by by purity be 4N and with
On Bi, Sb, Te, Se simple substance mixed according to stoichiometric ratio after, vacuum melting forms.
As a further improvement of the present invention, the p-type Bi x Sb 2-x Te 3-y Se y The detailed process of alloy pig preparation are as follows: press
Bi, Sb, Te, Se simple substance raw material that purity is 4N or more is weighed according to stoichiometric ratio to be placed in the glass tube of an end closure, with
Charged glass tube is fixed on the pipe support in rocking furnace by vacuum-pumping and sealing afterwards, and rocking furnace heating is until reach setting temperature
Melting is carried out after 650-710 DEG C of degree, smelting time is 10-30 min, and melting terminates, and takes out pipe support rapidly, completely solidifying in alloy
Gu pipe support is beaten before and drives bubble in glass tube, and catching up with the bubble time is 0.5-3min, is then cooled to room temperature glass tube, i.e.,
P-type Bi can be obtained x Sb 2-x Te 3-y Se y Alloy pig.
The present invention obtains qualified tellurium bismuthino thermoelectric material by the way that the alloy pig after melting is directly carried out hot pressing twice.
Preparation method of the present invention is simple, high production efficiency, and the electric property and mechanical performance of obtained product significantly improve.
Specific embodiment
Technical solution is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention proposes a kind of preparation method of tellurium bismuthino thermoelectric material, first by p-type Bi x Sb 2-x Te 3-y Se y Alloy pig carries out
Hot pressing forms an alloy block, wherein 0.4≤x≤ 0.52,0≤y≤0.15；Again by an alloy block with its length side
90 ° of placements are overturn to for axis, secondary hot pressing is carried out, obtains tellurium bismuthino thermoelectric material.
The present invention is first by p-type Bi x Sb 2-x Te 3-y Se y Alloy pig carries out a hot pressing are as follows: according to the big of hot pressing die
It is small, corresponding length is intercepted from alloy pig, carries out a hot pressing.After an alloy deblocking temperature is cooling, by an alloy block
Two 0.5 ~ 3mm of Bottoming of length direction, then be along its length that axis overturns 90 ° and is placed in hot pressing die by it, it carries out
Secondary hot pressing obtains tellurium bismuthino thermoelectric material.
In certain embodiments of the present invention, the temperature of a hot pressing is 250 ~ 350 DEG C, pressure is 5 ~ 30MPa.
In certain embodiments of the present invention, the heating rate of a hot pressing is 5 ~ 10 DEG C/min.
In certain embodiments of the present invention, the time of a hot pressing is 50 ~ 60min.
In certain embodiments of the present invention, the temperature of the secondary hot pressing is 350 ~ 450 DEG C, pressure is 15 ~ 45MPa.
In certain embodiments of the present invention, the heating rate of the secondary hot pressing is 10 ~ 20 DEG C/min.
In certain embodiments of the present invention, the time of the secondary hot pressing is 5 ~ 60min.
P-type Bi x Sb 2-x Te 3-y Se y The preparation of alloy pig be by by purity be 4N or more Te, Bi, Sb simple substance according to
After stoichiometric ratio mixing, melting is formed under vacuum conditions.
Above-mentioned p-type Bi x Sb 2-x Te 3-y Se y The specific forming process of alloy pig are as follows: weighing purity according to stoichiometric ratio is 4N
Or more Bi, Sb, Te, Se simple substance raw material is placed in the glass tube of an end closure, sealing is subsequently vacuumed out, by charged glass
Glass pipe is fixed on the pipe support in rocking furnace, and rocking furnace heating is up to carrying out melting, melting after reaching 650-710 DEG C of set temperature
Time is 10-30 min, and melting terminates, takes out pipe support rapidly, beat pipe support before alloy solidifies completely and drive in glass tube
Bubble, catching up with the bubble time is 0.5-3min, is then cooled to room temperature glass tube, can obtain p-type Bi x Sb 2-x Te 3-y Se y Alloy
Ingot.
The preparation method of tellurium bismuthino thermoelectric material provided by the invention directly carries out the alloy pig obtained after melting twice
Powder processed is melted without area or be crushed to hot pressing, so that it may obtain tellurium bismuthino thermoelectric material of good performance.Method provided by the invention,
Simple process, high production efficiency, the product electric property and mechanical performance of preparation significantly improve.
Embodiment 1.
P-type Bi0.52Sb1.48Te2.85Se0.15The preparation method of tellurium bismuthino thermoelectric material, includes the following steps.
The first step, molten alloy ingot.
According to p-type Bi0.52Sb1.48Te2.85Se0.15Stoichiometric ratio weigh purity be 4N Bi, Sb, Te, Se simple substance in
In glass tube, by glass tube vacuum-pumping and sealing.Then the glass tube after sealing two ends is fixed on pipe support and is placed in rocking furnace
Melting 10min at a temperature of 710 DEG C inherent.Melting terminates, and takes out pipe support rapidly, beats pipe from lower to upper before alloy solidifies completely
Frame drives the bubble in glass tube, and catching up with the bubble time is 3min, is then cooled to room temperature, smashes glass tube and takes out alloy pig, i.e.,
P-type Bi can be obtained0.52Sb1.48Te2.85Se0.15Alloy pig.
Second step, forging and stamping processing.
By p-type Bi0.52Sb1.48Te2.85Se0.15Alloy pig interception is placed in hot-pressing processing in mold, is heated up with 5 DEG C/min fast
Degree rises to 250 DEG C of hot pressing of progress and forms an alloy block, and the soaking time of a hot pressing is 50min, and pressure is
30MPa.Alloy block is overturn into 90 ° of placements by axis of its length direction, cuts 0.5mm, respectively end to end along its length with 10
DEG C/min heating rate rises to 450 DEG C of progress secondary hot pressings, the soaking time of secondary hot pressing is 5min, pressure 45MPa, i.e.,
Obtain p-type Bi0.52Sb1.48Te2.85Se0.15Tellurium bismuthino thermoelectric material.
The thermoelectricity capability test result of the preparation-obtained sample of preparation method according to the invention is shown, originates melting sample
The conductivity of product is 940 S/cm, and electromotive force rate is 180 μ V/K, and the conductivity of sample is 820 S/cm after hot pressing twice,
Electromotive force rate value is 206 μ V/K.The bending tensile strength of sample has been increased to 50 after hot pressing twice by 30 MPa before hot pressing
MPa。
As a comparison, same composition raw material passes through 6h ball milling, and the conductivity obtained after 360 DEG C of hot pressing 2h is 460
S/cm, electromotive force rate are 231 μ V/K.The electrical property of the preparation-obtained sample of preparation method according to the invention is much better than ball milling
Obtained sample.
Embodiment 2.
P-type Bi0.4Sb1.6Te3The preparation method of tellurium bismuthino thermoelectric material, includes the following steps.
The first step, molten alloy ingot.
According to p-type Bi0.4Sb1.6Te3Stoichiometric ratio weigh Bi, Sb, Te simple substance that purity is 4N in glass tube, will
Glass tube vacuum-pumping and sealing.Then the glass tube after sealing two ends is fixed on pipe support and is placed in rocking furnace in 680 DEG C of temperature
Spend lower melting 20min.Melting terminates, and takes out pipe support rapidly, beats pipe support from lower to upper before alloy solidifies completely and drives glass
Bubble in pipe, catching up with the bubble time is 1min, is then cooled to room temperature, smashes glass tube and takes out alloy pig, can obtain p-type
Bi0.4Sb1.6Te3Alloy pig.
Second step, forging and stamping processing.
By p-type Bi0.4Sb1.6Te3Alloy pig interception is placed in hot-pressing processing in mold, is risen to 10 DEG C/min heating rate
300 DEG C of hot pressing of progress form an alloy block, and the soaking time of a hot pressing is 55min, pressure 15MPa.It will be primary
Alloy block overturns 90 ° of placements by axis of its length direction, cuts 3mm, respectively end to end along its length with 20 DEG C/min heating rate
Rise to 400 DEG C of progress secondary hot pressings, the soaking time of secondary hot pressing is 30min, and pressure is 30MPa to get p-type is arrived
Bi0.4Sb1.6Te3Tellurium bismuthino thermoelectric material.
The thermoelectricity capability test result of the preparation-obtained sample of preparation method according to the invention is shown, originates melting sample
The conductivity of product is 1000 S/cm, and electromotive force rate is 175 μ V/K, and the conductivity of sample is 910 S/ after secondary hot pressing
Cm, electromotive force rate value are 196 μ V/K.The bending tensile strength of sample is increased to 60 after hot pressing twice by 35 MPa before hot pressing
MPa。
As a comparison, same composition raw material passes through 6h ball milling, and the conductivity obtained after 360 DEG C of hot pressing 2h is 560
S/cm, electromotive force rate are 217 μ V/K.The electrical property of the preparation-obtained sample of preparation method according to the invention is much better than ball milling
Obtained sample.
Embodiment 3.
P-type Bi0.48Sb1.52Te2.9Se0.1The preparation method of tellurium bismuthino thermoelectric material, includes the following steps.
The first step, molten alloy ingot.
According to p-type Bi0.48Sb1.52Te2.9Se0.1Stoichiometric ratio weigh purity be 4N Bi, Sb, Te, Se simple substance in glass
In glass pipe, by glass tube vacuum-pumping and sealing.Then the glass tube after sealing two ends is fixed on pipe support and is placed in rocking furnace
Melting 30min at a temperature of 650 DEG C.Melting terminates, and takes out pipe support rapidly, beats pipe support from lower to upper before alloy solidifies completely
The bubble in glass tube is driven, catching up with the bubble time is 0.5min, is then cooled to room temperature, smashes glass tube and takes out alloy pig, i.e.,
P-type Bi can be obtained0.48Sb1.52Te2.9Se0.1Alloy pig.
Second step, forging and stamping processing.
By p-type Bi0.48Sb1.52Te2.9Se0.1Alloy pig interception is placed in hot-pressing processing in mold, with 8 DEG C/min heating rate
It rises to hot pressing of 350 DEG C of progress and obtains an alloy block, the soaking time of a hot pressing is 60min, pressure 5MPa.It will
Alloy block overturns 90 ° of placements by axis of its length direction, respectively cuts 2mm end to end along its length, with 15 DEG C/min heating
Speed rises to 350 DEG C of progress secondary hot pressings, and the soaking time of secondary hot pressing is 60min, pressure is 15MPa to get to p-type
Bi0.48Sb1.52Te2.9Se0.1Tellurium bismuthino thermoelectric material.
The thermoelectricity capability test result of the preparation-obtained sample of preparation method according to the invention is shown, originates melting sample
The conductivity of product is 1100 S/cm, and electromotive force rate is 167 μ V/K, and the conductivity of sample is 950 S/ after secondary compacting
Cm, electromotive force rate value are 193 μ V/K.The bending tensile strength of sample is increased to 55 after hot pressing twice by 28 MPa before hot pressing
MPa。
As a comparison, same composition raw material passes through 6h ball milling, and the conductivity obtained after 360 DEG C of hot pressing 2h is 680
S/cm, electromotive force rate are 227 μ V/K.The electrical property of the preparation-obtained sample of preparation method according to the invention is much better than ball milling
Obtained sample.
The present invention obtains qualified tellurium bismuthino thermoelectric material by the way that the alloy pig after melting is directly carried out hot pressing twice.
Preparation method of the present invention is simple, high production efficiency, and the electric property and mechanical performance of obtained product significantly improve.
Although for illustrative purposes, the preferred embodiment of the present invention is had been disclosed, but the ordinary skill people of this field
Member will realize without departing from the scope and spirit of the invention as disclosed by the appended claims, various to change
Into, increase and replace be possible.
Claims (8)
1. a kind of preparation method of tellurium bismuthino thermoelectric material, it is characterised in that:
First by p-type BixSb2-xTe3-ySeyAlloy pig carries out a hot pressing, forms an alloy block, wherein 0.4≤x≤0.52,0
≤y≤0.15；
An alloy block is overturn into 90 ° of placements by axis of its length direction again, secondary hot pressing is carried out, obtains tellurium bismuthino thermoelectricity material
Material；
The p-type BixSb2-xTe3-ySeyAlloy pig be by by purity be 4N or more Bi, Sb, Te, Se simple substance according to chemistry
After metering is than mixing, vacuum melting is formed；
The p-type BixSb2-xTe3-ySeyAlloy pig preparation detailed process are as follows: according to stoichiometric ratio weigh purity be 4N and with
On Bi, Sb, Te, Se simple substance raw material be placed in the glass tube of an end closure, sealing is subsequently vacuumed out, by charged glass tube
It is fixed on the pipe support in rocking furnace, rocking furnace heating is up to carrying out melting, smelting time after reaching 650-710 DEG C of set temperature
For 10-30min, melting terminates, and takes out pipe support rapidly, and pipe support is beaten before alloy solidifies completely and drives bubble in glass tube,
Catching up with the bubble time is 0.5-3min, is then cooled to room temperature glass tube, can obtain p-type BixSb2-xTe3-ySeyAlloy pig.
2. the preparation method of tellurium bismuthino thermoelectric material according to claim 1, it is characterised in that: the temperature of a hot pressing
Degree is 250~350 DEG C, pressure is 5~30MPa.
3. the preparation method of tellurium bismuthino thermoelectric material according to claim 2, it is characterised in that: the liter of a hot pressing
Warm rate is 5~10 DEG C/min.
4. the preparation method of tellurium bismuthino thermoelectric material according to claim 2, it is characterised in that: a hot pressing when
Between be 50~60min.
5. the preparation method of tellurium bismuthino thermoelectric material according to claim 1, it is characterised in that: the temperature of the secondary hot pressing
Degree is 350~450 DEG C, pressure is 15~45MPa.
6. the preparation method of tellurium bismuthino thermoelectric material according to claim 5, it is characterised in that: the liter of the secondary hot pressing
Warm rate is 10~20 DEG C/min.
7. the preparation method of tellurium bismuthino thermoelectric material according to claim 5, it is characterised in that: the secondary hot pressing when
Between be 5~60min.
8. the preparation method of tellurium bismuthino thermoelectric material according to claim 1, it is characterised in that: an alloy block is long
Two ends in degree direction need to cut off 0.5~3mm respectively.
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| CN110098310B (en) * | 2018-01-30 | 2023-11-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of SnSe-based thermoelectric material oriented polycrystal |
| 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 |
| CN114835495B (en) * | 2021-02-01 | 2024-02-23 | 中国科学院宁波材料技术与工程研究所 | Preferred orientation n-type bismuth telluride sintered material and preparation method and application thereof |
| CN115141019B (en) * | 2022-07-15 | 2023-09-08 | 湖北赛格瑞新能源科技有限公司 | Method for preparing p-type bismuth telluride-based thermoelectric material by utilizing accumulated hot heading |
| CN116891380B (en) * | 2023-07-20 | 2024-08-30 | 六盘水师范学院 | Preparation method of Se-optimized high-purity bismuth telluride antimony-doped thermoelectric material |
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