CN112342619A - Method for optimizing carrier concentration of thermoelectric material - Google Patents

Method for optimizing carrier concentration of thermoelectric material Download PDF

Info

Publication number
CN112342619A
CN112342619A CN202011069673.4A CN202011069673A CN112342619A CN 112342619 A CN112342619 A CN 112342619A CN 202011069673 A CN202011069673 A CN 202011069673A CN 112342619 A CN112342619 A CN 112342619A
Authority
CN
China
Prior art keywords
melting
ingot
carrier concentration
zone
thermoelectric material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011069673.4A
Other languages
Chinese (zh)
Other versions
CN112342619B (en
Inventor
翟仁爽
刘凌波
吴永庆
阮炜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Forerunner Thermoelectric Technology Co ltd
Original Assignee
Zhejiang Forerunner Thermoelectric Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Forerunner Thermoelectric Technology Co ltd filed Critical Zhejiang Forerunner Thermoelectric Technology Co ltd
Priority to CN202011069673.4A priority Critical patent/CN112342619B/en
Publication of CN112342619A publication Critical patent/CN112342619A/en
Application granted granted Critical
Publication of CN112342619B publication Critical patent/CN112342619B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
    • C30B28/08—Production of homogeneous polycrystalline material with defined structure from liquids by zone-melting
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention belongs to the field of thermoelectric materials, and provides a method for optimizing the carrier concentration of a thermoelectric material, which aims to solve the problems of very slow material development process and low efficiency caused by very limited optimization process of the carrier concentration n of the thermoelectric material. The method is simple and efficient, saves a large amount of manpower and material resources in the material development link, reduces the development cost, and accelerates the engineering application of material research.

Description

Method for optimizing carrier concentration of thermoelectric material
Technical Field
The invention belongs to the field of thermoelectric materials, and particularly relates to a method for optimizing carrier concentration of a thermoelectric material.
Background
At the present stage, a large amount of low-grade heat energy is directly discharged as waste heat, so that the energy utilization rate of the human society is low. The thermoelectric device can directly realize the conversion of heat energy and electric energy, and has unique application advantages due to small volume, no noise and no moving parts. The refrigerating efficiency of thermoelectric devices mainly depends on the dimensionless thermoelectric figure of merit of material, zT ═ alpha2And sigma T/kappa, wherein alpha is the Seebeck coefficient of the material, sigma is the electric conductivity, and kappa is the thermal conductivity. Alpha is alpha2σ is called the Power Factor (PF) to measure the electrical properties of the material. Note that α, σ, and κ are all tightly coupled to the carrier concentration n inside the material. Generally, as n increases, α decreases and σ increases. Kappa is mainly composed of two parts, electron thermal conductivity kappaeAnd lattice thermal conductivity κlThe former is increased with the increase of n, and the latter can be relatively independently regulated and controlled. Therefore, the thermoelectric figure of merit of the material is generally optimized by first optimizing the carrier concentration n inside the material, so that the power factor PF is excellent; then, point defect regulation is utilized, and means such as multi-scale microstructure, nanocrystallization and the like are introduced, so that the lattice thermal conductivity kappa which can be relatively independently regulated and controlled is reducedl. In particular, the band structure of some materials can be adjusted so that the Seebeck coefficient is further increased, referred to as "band engineering". In summary, optimizing the carrier concentration n of a material is the first step, and is the most important step, in optimizing the thermoelectric performance of the material.
At present, the optimization process of the carrier concentration n of the thermoelectric material is very limited, and different elements are mainly doped on the same substrate, so that different doping amounts are designed. For example, the following steps are carried out: for n optimization of the bismuth telluride matrix, 5 components with different Cu doping amounts are designed to obtain a relation curve of materials zT corresponding to different n, and the optimized n is obtained through quadratic fitting, so that complicated processes such as weighing, sample preparation, cutting, testing and the like are required for 5 times. Assuming that the experimental design range is not in accordance with the expectation, n-zT does not have a vertex, samples of n in different ranges are required to be supplemented, and weighing, sample preparation, cutting, testing and the like are carried out again. Such a cumbersome process makes the material development process very slow and inefficient.
Disclosure of Invention
In order to solve the problems that the optimization process of the thermoelectric material carrier concentration n is very limited, so that the material development process is very slow and the efficiency is low, the invention provides the method for optimizing the carrier concentration of the thermoelectric material, which is simple and efficient, saves a large amount of manpower and material resources in the material development link, reduces the development cost and accelerates the engineering application of material research.
The invention utilizes the liquid-solid phase transition and the segregation phenomenon generated in the normal solidification process to obtain samples with different doping amounts, namely different carrier concentrations n in the same ingot. Segregation phenomenon means that solute atoms have different solid solubility in a solid solvent and a liquid solvent, and when a liquid phase starts to crystallize locally into a solid phase, a part of solute atoms cannot be dissolved into a solid phase after crystallization (segregation coefficient is less than 1), and therefore the doping concentration of the part is lower than the equilibrium concentration. For the zone melting process, the doping concentration will vary according to the following equation:
Figure BDA0002713642510000021
Figure BDA0002713642510000022
wherein C is the doping content in the solid phase, k is the segregation coefficient, C0For the equilibrium doping concentration (average doping concentration for the material design), g is the solidified portion length, X is the total ingot length, and l is the melt zone length. Therefore, by adjusting the above parameters and the number of times of zone melting (the effect of the multi-melting zone is consistent with the effect of the multi-zone melting), a sufficient concentration gradient can be obtained on one ingot. And calculating the optimal cast ingot position of the PF through simple and easy Seebeck coefficient and quick conductivity scanning, and testing n of the cast ingot position to obtain the optimized carrier concentration.
The invention is realized by the following technical scheme: a method for optimizing carrier concentration of thermoelectric material comprises the following steps:
(1) carrying out one or more zone melting on the thermoelectric material substrate to prepare an ingot, or one zone melting on the ingot in a plurality of melting zones to prepare the ingot in a component gradient manner;
the multiple zone melting is to perform secondary zone melting and third zone melting on the ingot subjected to zone melting once again, the gradient of component distribution is more obvious according to the segregation theory, and a theoretical curve of the component distribution of the multiple zone melting disclosed in the book 'zone melting' of w.g.pfann is shown in fig. 5. In addition, the effect of single zone melting in the multi-melting zone is equal to that of multiple zone melting, and essentially the same part of the ingot is subjected to multiple zone melting processes to generate multiple segregation effects, so that the components generate obvious gradients.
The thermoelectric material matrix is one or more matrixes, and the batch material development is carried out by zone melting at the same time. The currently developed screening method for thermoelectric materials can complete the development of more than 20 materials within 2 days; whereas a typical thermoelectric material has a one-monday cycle for which the material is tested.
The melting zone heating mode of zone melting comprises resistance wire heating, optical heating and induction heating.
The single-melting zone melting or the multi-melting zone melting is mainly determined by the segregation coefficient (k) of the base material. Different zone melting modes need to be selected so that the ingot generates a larger performance gradient.
The preparation method of the zone melting ingot is shown in figure 1 as follows:
(1.1) crushing a base raw material and a doping element block;
(1.2) weighing the raw materials and the doping elements in the step (1) according to the stoichiometric ratio of each element in the matrix component, filling the mixture into a clean die,
according to the matrix component to be researched, the higher the difference value between the segregation coefficient of the doped proper element and 1 is, the better the doped amount is, the doping amount is not more than 10% of the molar content of the matrix component, the raw materials in the step (1) in the corresponding proportion are weighed, and the raw materials are filled into a cleaned mould
The top of the mould is flat-bottomed and non-conical so as to obtain a regular cylindrical zone-melting ingot with a large-range carrier concentration distribution
The die material comprises high-melting-point ceramics such as quartz, graphite, magnesium oxide and the like. When quartz is used as a mold and a material (containing Mg, Pb, etc.) which is easy to react with quartz is loaded, high-temperature carbon coating treatment is carried out.
Preferably, the washing is carried out using a front mold: pouring dilute nitric acid into a mold, ultrasonically oscillating for 15-20 min, pouring out the nitric acid, cleaning the nitric acid twice with clear water and once with absolute ethyl alcohol, and then putting the mold into an oven to dry for 12 hours at 120 ℃ for later use.
(1.3) pumping the vacuum degree of the mould in the step (2) to be less than or equal to 10-3Pa, sealing the mould by using a high heat source;
the high heat source is typically an oxyhydrogen flame or an acetylene flame.
And (1.4) placing the sealed die into a swinging smelting furnace to be smelted for 10-12h to obtain a polycrystalline ingot, and cooling the polycrystalline ingot to room temperature along with the furnace.
Preferably, smelting is carried out in a swing smelting furnace at 650-1000 ℃ for 10-12h, and swing is carried out all the time in the smelting process to ensure that the raw materials are fully mixed.
And (1.5) placing the polycrystalline ingot obtained in the step (4) into a vertical zone melting furnace for zone melting growth to prepare a thermoelectric material zone melting ingot.
The zone melting temperature is higher than the melting point of the material by 50K, the length of a melting zone is 1-6 cm, the furnace body moves from the tip of the polycrystalline ingot to the other end, and the furnace body is cooled to room temperature after zone melting.
(2) And carrying out scanning test on the Seebeck coefficient alpha and the conductivity sigma of the ingot along the zone melting direction, and sampling and testing the ingot part with the highest electric power factor to obtain the optimized carrier concentration.
The calculation formula of the maximum electric power factor is PF ═ alpha2σ。
The method adopts single-melting zone one-time or multi-time zone melting or multi-melting zone one-time zone melting to prepare the thermoelectric material matrix to be researched by component gradient ingot casting, applies high-flux screening technology to the thermoelectric material to avoid the process of repeatedly preparing samples for many times in the development of the thermoelectric material, prepares the ingot inherently having doping concentration gradient by segregation phenomenon generated by zone melting method, and non-destructively scans the electrical property of the ingot to obtain important physical parameters in the development of the thermoelectric material, namely optimized carrier concentration.
Compared with the prior art, the invention has the beneficial effects that: the development period of the thermoelectric material is greatly shortened, and the development cost is reduced.
Drawings
FIG. 1 is a flow chart of a method of making a thermoelectric zone-melting ingot of the present invention;
FIG. 2 shows Seebeck coefficients of different portions of a molten ingot of a bismuth N-telluride base region obtained by single zone melting of a single melting zone prepared in example 1;
FIG. 3 shows the electrical conductivities of different parts of a molten ingot of a bismuth N-telluride base region obtained by single zone melting of a single melting zone prepared in example 1;
FIG. 4 shows power factors of different parts of a molten ingot of a bismuth N-telluride base region obtained by single zone melting of a single melting zone prepared in example 1;
FIG. 5 is a disclosed multiple zone melting theoretical compositional gradient profile;
FIG. 6 shows Seebeck coefficients of different portions of a molten ingot of a P-type bismuth telluride base region obtained by single zone melting of a single melting zone prepared in example 2;
FIG. 7 shows the electrical conductivities of different parts of a molten ingot of a P-type bismuth telluride base region obtained by single zone melting of a single melting zone prepared in example 2;
FIG. 8 is a graph showing power factors at different positions of a molten ingot of a P-type bismuth telluride base region obtained by single zone melting of a single melting zone prepared in example 2;
FIG. 9 is the Seebeck coefficients of different portions of a molten ingot of a bismuth N-telluride base region obtained by secondary zone-melting of a single-melted zone prepared in example 3;
FIG. 10 is the electrical conductivities of different parts of the single-melt-zone secondary zone-melting bismuth-telluride-base-region-obtained fusion-cast ingot of example 3;
fig. 11 shows power factors at different positions of a single-melt-zone secondary zone-melting bismuth-telluride-base-region-obtained fusion-cast ingot of example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the present invention is not limited to the following examples, and the raw materials used in the examples are commercially available or can be prepared by a conventional method.
Example 1
(1) Preparing a casting ingot of the N-type bismuth telluride base region by adopting a single melting region and single zone melting;
(1.1) crushing raw materials of Bi blocks, Te blocks, Se blocks and I blocks;
(1.2) sealing one end of a quartz tube with the inner diameter of 28mm and the length of about 900mm by oxyhydrogen flame to form a flat bottom, pouring dilute nitric acid into the quartz tube, ultrasonically oscillating for 20min, pouring out the nitric acid, cleaning twice by using clear water, cleaning once by using absolute ethyl alcohol, and then putting the quartz tube into an oven to dry for 12 hours at 120 ℃ for later use;
according to the N-type conventional column chemical formula Bi2Te2.7Se0.3Weighing 1000g of the raw materials in the step (1) according to the stoichiometric ratio of the elements, putting the raw materials into a dried quartz tube, and doping 10g of the element I.
(1.3) pumping the vacuum degree of the quartz tube in the step (2) to 10-3Pa, sealing the other end of the quartz tube by using oxyhydrogen flame, and forming a flat bottom;
(1.4) putting the quartz tube in the step (3) into a rotary smelting furnace at 800 ℃ to be smelted for 10 hours, swinging all the time in the smelting process to ensure that the raw materials are fully mixed, and cooling to room temperature to obtain a polycrystalline ingot;
and (1.5) placing the polycrystalline ingot obtained in the step (4) on a vertical zone melting furnace for zone melting growth, wherein the zone melting temperature is 650 ℃, the growth speed (moving speed) is 25mm/h, the length of a melting zone is 5cm, and after the polycrystalline ingot is zone-melted from one end to the other end, cooling to room temperature to obtain the bismuth telluride base zone melting ingot.
(2) And carrying out scanning test on the Seebeck coefficient alpha and the conductivity sigma of the ingot along the zone melting direction, and sampling and testing the ingot part with the highest electric power factor to obtain the optimized carrier concentration.
The obtained doping concentration gradient of the casting ingot of the N-type bismuth telluride base region prepared by single zone melting is obvious. As shown in fig. 2, the Seebeck coefficient is always reduced along with the direction of zone melting, which indicates that n is always increased along with the progress of zone melting; the conductivity continued to increase as shown in FIG. 3, and as shown in FIG. 4, the optimum carrier concentration was obtained at 17cm from the start of zone-melting, corresponding to a power factor PF of 50X 10 at maximum-4Wm-1K-2。
Finally, the test carrier concentration of the sample at the corresponding position of the cut is 2.5 multiplied by 1019cm-3. Thus obtaining Bi2Te2.7Se0.3Corresponding to an optimum carrier concentration of 2.5X 1019cm-3Nearby.
Example 2
(1) Preparing a P-type bismuth telluride base region casting ingot by adopting a single melting region and single zone melting;
(1.1) crushing raw materials of Bi blocks, Sb blocks, Te blocks and Fe particles;
(1.2) sealing one end of a quartz tube with the inner diameter of 28mm and the length of about 900mm by oxyhydrogen flame to form a flat bottom, pouring dilute nitric acid into the quartz tube, ultrasonically oscillating for 20min, pouring out the nitric acid, cleaning twice by using clear water, cleaning once by using absolute ethyl alcohol, and then putting the quartz tube into an oven to dry for 12 hours at 120 ℃ for later use;
according to the formula of P-type Bi1.3Sb0.7Te3Weighing 1000g of the raw materials in the step (1) according to the stoichiometric ratio of the elements, putting the raw materials into a dried quartz tube, and doping 10g of Fe element.
(1.3) pumping the vacuum degree of the quartz tube in the step (2) to 10-3Pa, sealing the other end of the quartz tube by using oxyhydrogen flame, and forming a flat bottom;
(1.4) putting the quartz tube in the step (3) into a rotary smelting furnace at 800 ℃ to be smelted for 10 hours, swinging all the time in the smelting process to ensure that the raw materials are fully mixed, and cooling to room temperature to obtain a polycrystalline ingot;
and (1.5) placing the polycrystalline ingot obtained in the step (4) on a vertical zone melting furnace for zone melting growth, wherein the zone melting temperature is 650 ℃, the growth speed (moving speed) is 25mm/h, the length of a melting zone is 4cm, and after the polycrystalline ingot is zone-melted from one end to the other end, cooling to room temperature to obtain the bismuth telluride base zone melting ingot.
(2) And carrying out scanning test on the Seebeck coefficient alpha and the conductivity sigma of the ingot along the zone melting direction, and sampling and testing the ingot part with the highest electric power factor to obtain the optimized carrier concentration.
Preparing a P-type bismuth telluride base region casting ingot by single zone melting, and preparing a P-type bismuth telluride base region casting ingot by single zone meltingThe more obvious doping concentration gradient is obtained. As shown in fig. 6, the Seebeck coefficient increases overall with the direction of zone-melting, indicating that n decreases as zone-melting progresses; therefore, the conductivity continues to decrease as shown in fig. 7. Finally, the optimal carrier concentration is obtained when the zone melting is started to be 12cm, and the corresponding power factor PF is the maximum and reaches 31.8 multiplied by 10-4Wm-1K-2。
Finally, the test carrier concentration of the sample at the corresponding position of the cut is 1.1 multiplied by 1019cm-3. Thus obtaining Bi1.3Sb0.7Te3Corresponding to an optimum carrier concentration of 1.1X 1019cm-3Nearby.
Example 3
(1) Preparing a casting ingot of an N-type bismuth telluride base region by adopting a single melting region and secondary zone melting;
(1.1) crushing raw materials of Bi blocks, Te blocks, Se blocks and Cu particles;
(1.2) sealing one end of a quartz tube with the inner diameter of 28mm and the length of about 900mm by oxyhydrogen flame to form a flat bottom, pouring dilute nitric acid into the quartz tube, ultrasonically oscillating for 20min, pouring out the nitric acid, cleaning twice by using clear water, cleaning once by using absolute ethyl alcohol, and then putting the quartz tube into an oven to dry for 12 hours at 120 ℃ for later use;
according to the N-type conventional column chemical formula Bi2Te2.3Se0.7Weighing 1000g of the raw materials in the step (1) according to the stoichiometric ratio of the elements, putting the raw materials into a dried quartz tube, and doping 10g of Cu element.
(1.3) pumping the vacuum degree of the quartz tube in the step (2) to 10-3Pa, sealing the other end of the quartz tube by using oxyhydrogen flame, and forming a flat bottom;
(1.4) putting the quartz tube in the step (3) into a rotary smelting furnace at 800 ℃ to be smelted for 10 hours, swinging all the time in the smelting process to ensure that the raw materials are fully mixed, and cooling to room temperature to obtain a polycrystalline ingot;
and (1.5) placing the polycrystalline ingot obtained in the step (4) on a vertical zone melting furnace for zone melting growth, wherein the zone melting temperature is 650 ℃, the growth speed (moving speed) is 25mm/h, the length of a melting zone is 5cm, and after the polycrystalline ingot is zone-melted from one end to the other end, cooling to room temperature to obtain the bismuth telluride base zone melting ingot.
(2) And carrying out scanning test on the Seebeck coefficient alpha and the conductivity sigma of the ingot along the zone melting direction, and sampling and testing the ingot part with the highest electric power factor to obtain the optimized carrier concentration.
The doping concentration gradient obtained by the casting ingot of the N-type bismuth telluride base region prepared by the secondary zone melting is very obvious. As shown in fig. 9, the Seebeck coefficient decreases with the direction of zone-melting, indicating that n increases with the progress of zone-melting; while the conductivity continues to increase (fig. 10); as shown in FIG. 11, the optimum carrier concentration was obtained at 2cm from the start of zone-melting, and the corresponding power factor PF was the maximum and reached 24X 10-4Wm-1K-2。
Finally, the test carrier concentration of the sample at the corresponding position of the cut is 3.2 multiplied by 1019cm-3. Thus obtaining Bi2Te2.3Se0.7Corresponding optimum carrier concentration of 3.2 × 1019cm-3Nearby.
The most important physical parameters in the development of the thermoelectric material are obtained only by once weighing, zone melting, sample preparation and testing, and the efficiency of material development is greatly improved. Meanwhile, due to the nondestructive testing of the ingot casting performance, the rest parts except the cylinder with the length of about 1cm which is finally cut can be recycled, so that the raw materials used for material development are greatly saved.

Claims (10)

1. A method for optimizing carrier concentration of a thermoelectric material is characterized by comprising the following steps:
(1) carrying out one or more zone melting on the thermoelectric material substrate to prepare an ingot, or one zone melting on the ingot in a plurality of melting zones to prepare the ingot in a component gradient manner;
(2) and carrying out scanning test on the Seebeck coefficient alpha and the conductivity sigma of the ingot along the zone melting direction, and sampling and testing the ingot part with the highest electric power factor to obtain the optimized carrier concentration.
2. The method for optimizing carrier concentration of thermoelectric material as claimed in claim 1, wherein the thermoelectric material matrix in step (1) is one or more matrices.
3. The method for optimizing the carrier concentration of the thermoelectric material as claimed in claim 1, wherein the zone heating manner of the zone melting in the step (1) comprises resistance wire heating, optical heating and induction heating.
4. The method for optimizing the carrier concentration of the thermoelectric material as claimed in claim 1, wherein the method for preparing the zone melting ingot comprises the following steps:
(1.1) crushing a base raw material and a doping element block;
(1.2) weighing the required matrix component raw materials and doping elements, and filling the mixture into a clean die;
(1.3) pumping the vacuum degree of the mould in the step (2) to be less than or equal to 10-3Pa, sealing the mould by using a high heat source;
(1.4) putting the sealed die into a swinging smelting furnace to be smelted for 10-12h to obtain a polycrystalline ingot;
and (1.5) placing the polycrystalline ingot obtained in the step (4) into a vertical zone melting furnace for zone melting growth to prepare a thermoelectric material zone melting ingot.
5. The method for optimizing carrier concentration of thermoelectric material as claimed in claim 4, wherein the higher the segregation coefficient of the doping element in step (1) is from 1, the better.
6. A method of optimizing carrier concentration in a thermoelectric material as set forth in claim 4 or 5, characterized in that the doping element is doped in an amount of 10 mol% or less based on the matrix component.
7. The method for optimizing carrier concentration in thermoelectric material as claimed in claim 4, wherein in step (1.2), the top of the mold is flat bottom, and the mold material comprises quartz, graphite, and high melting point ceramics.
8. The method for optimizing carrier concentration of thermoelectric material as claimed in claim 4, wherein the high heat source in step (1.3) is generally oxyhydrogen flame or acetylene flame.
9. The method for optimizing the carrier concentration of the thermoelectric material as claimed in claim 4, wherein the melting temperature of step (1.4) is higher than the melting point of the material by 50K, and the length of the melting zone is 1-6 cm.
10. The method of claim 1, wherein step (2) comprises optimizing the carrier concentration with a maximum electrical power factor PF ═ α2σ。
CN202011069673.4A 2020-09-30 2020-09-30 Method for optimizing carrier concentration of thermoelectric material Active CN112342619B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011069673.4A CN112342619B (en) 2020-09-30 2020-09-30 Method for optimizing carrier concentration of thermoelectric material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011069673.4A CN112342619B (en) 2020-09-30 2020-09-30 Method for optimizing carrier concentration of thermoelectric material

Publications (2)

Publication Number Publication Date
CN112342619A true CN112342619A (en) 2021-02-09
CN112342619B CN112342619B (en) 2022-03-22

Family

ID=74361531

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011069673.4A Active CN112342619B (en) 2020-09-30 2020-09-30 Method for optimizing carrier concentration of thermoelectric material

Country Status (1)

Country Link
CN (1) CN112342619B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265700A (en) * 2021-05-19 2021-08-17 西华大学 Method for homogenizing solute of ingot, method for preparing ingot with uniform composition and alloy ingot
CN116804288A (en) * 2023-08-21 2023-09-26 杭州大和热磁电子有限公司 Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002021606A1 (en) * 2000-09-08 2002-03-14 Korea Institute Of Science And Technology The method manufacturing p-type bismuth telluride thermoelectric materials for the enhancement of the yield of high quality ingot
CN109671840A (en) * 2018-12-12 2019-04-23 浙江大学 A kind of construction method, the antimony tellurium seleno thermoelectric material of the antimony tellurium selenium matrix alloy for thermoelectric material
CN110002412A (en) * 2019-04-22 2019-07-12 武汉科技大学 A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material
CN110592417A (en) * 2019-09-27 2019-12-20 昆明贵金属研究所 High-flux preparation method of sliding electric contact material with gradient distribution of components
CN110616457A (en) * 2019-10-31 2019-12-27 云南北方昆物光电科技发展有限公司 Device and method for purifying indium antimonide region

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002021606A1 (en) * 2000-09-08 2002-03-14 Korea Institute Of Science And Technology The method manufacturing p-type bismuth telluride thermoelectric materials for the enhancement of the yield of high quality ingot
CN109671840A (en) * 2018-12-12 2019-04-23 浙江大学 A kind of construction method, the antimony tellurium seleno thermoelectric material of the antimony tellurium selenium matrix alloy for thermoelectric material
CN110002412A (en) * 2019-04-22 2019-07-12 武汉科技大学 A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material
CN110592417A (en) * 2019-09-27 2019-12-20 昆明贵金属研究所 High-flux preparation method of sliding electric contact material with gradient distribution of components
CN110616457A (en) * 2019-10-31 2019-12-27 云南北方昆物光电科技发展有限公司 Device and method for purifying indium antimonide region

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113265700A (en) * 2021-05-19 2021-08-17 西华大学 Method for homogenizing solute of ingot, method for preparing ingot with uniform composition and alloy ingot
CN113265700B (en) * 2021-05-19 2022-03-29 西华大学 Method for homogenizing solute of ingot, method for preparing ingot with uniform composition and alloy ingot
CN116804288A (en) * 2023-08-21 2023-09-26 杭州大和热磁电子有限公司 Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator
CN116804288B (en) * 2023-08-21 2023-12-12 杭州大和热磁电子有限公司 Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator

Also Published As

Publication number Publication date
CN112342619B (en) 2022-03-22

Similar Documents

Publication Publication Date Title
US7326851B2 (en) Pb-Ge-Te-compounds for thermoelectric generators or Peltier arrangements
CN112342619B (en) Method for optimizing carrier concentration of thermoelectric material
CN106711317B (en) A kind of sulfur family leaded object thermoelectric material and preparation method thereof
CN112342618B (en) Method for improving thermoelectric performance uniformity of bismuth telluride base region casting ingot
CN109616568B (en) N-type antimony trimagneside alloy thermoelectric material with high mobility and preparation method thereof
CN108231991A (en) A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat
CN106830940A (en) A kind of GeTe base high-performances thermoelectric material and preparation method thereof
CN107799646B (en) Alloy thermoelectric semiconductor material and preparation method thereof
CN110257667B (en) N-type antimony trimagneside alloy thermoelectric material and preparation thereof
CN111490148B (en) Preparation method of polycrystalline SnSe-based thermoelectric material
CN106571422A (en) Bismuth telluride based N type thermoelectric material and preparation method thereof
CN107235477A (en) A kind of N-type high-performance argyrodite thermoelectric material and preparation method thereof
CN107845724A (en) A kind of low cost environment friendly SnS base thermoelectricity materials and preparation method thereof
CN105990510B (en) A kind of copper seleno high performance thermoelectric material and preparation method thereof
CN107359231B (en) Low-heat-conduction Geranite thermoelectric material and preparation method thereof
CN108735887A (en) Mix antimony high-performance GeTe-PbTe solid solution thermoelectric materials and preparation method thereof
CN114561707B (en) Infrared heating zone smelting furnace and method for preparing N-type bismuth telluride alloy by using same
CN115537908A (en) Preparation method of high-performance bismuth telluride-based thermoelectric material
Aguiar et al. Growth and microstructural characterization of SnSe-SnSe2 composite
Zhao et al. Si3N4/fused quartz composite crucible with enhanced thermal conductivity for multicrystalline silicon ingot growth
Fiorito et al. A Possible Method for the Growth of Homogeneous Mercury Cadmium Telluride Single Crystals
CN112342617A (en) Bismuth telluride zone-melting ingot casting mold and using method thereof
CN108878635A (en) N-shaped PbSe-PbS base thermoelectricity material and preparation method thereof
CN116804288B (en) Preparation method of N-type bismuth telluride zone-melting cast ingot for thermoelectric refrigerator
CN115196965B (en) N-type bismuth telluride thermoelectric material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant