CN102694116A - Method for preparing thermoelectric material with P-type nano-structure and bismuth telluride matrix - Google Patents

Method for preparing thermoelectric material with P-type nano-structure and bismuth telluride matrix Download PDF

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CN102694116A
CN102694116A CN2012101737213A CN201210173721A CN102694116A CN 102694116 A CN102694116 A CN 102694116A CN 2012101737213 A CN2012101737213 A CN 2012101737213A CN 201210173721 A CN201210173721 A CN 201210173721A CN 102694116 A CN102694116 A CN 102694116A
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荆洪阳
陈岚
徐连勇
韩永典
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Tianjin University
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Abstract

The invention discloses a method for preparing a thermoelectric material with a P-type nano-structure and a Bi0.5Sb1.5Te3 matrix. The method includes synthesizing P-type Bi0.5Sb1.5Te3 compound nanometer powder from high-purity Bi powder (with purity of 99.99%), Sb powder and Te powder in a mechanical alloying (MA) manner; and sintering the Bi0.5Sb1.5Te3 precursor nanometer powder into the dense fine crystal thermoelectric material by a vacuum hot-pressing sintering (HP) method. The problem of volatility of elements such as Bi, Sb and Te in a melting state is avoided, and the material with uniform components and fine texture can be prepared. The granularity of the powder reaches a nanometer grade, phonon scattering is increased effectively, thermal conductivity is lowered, and the thermoelectric performance is enhanced.

Description

A kind of preparation method of P type nanostructure bismuth telluride based bulk thermoelectric material
Technical field
The invention relates to thermoelectric material, (Mechanical alloying, MA) combining vacuum heating-press sintering, (Hot Pressing, method HP) prepares nano-level P-type bismuth telluride-base (Bi to relate in particular to a kind of use mechanical alloying 0.5Sb 1.5Te 3) preparation method of block thermoelectric material.
Background technology
Thermoelectric material is to utilize thermoelectric effect, through the material internal carrier moving with heat energy and electric energy intercouple, each other the conversion one type of important functional material.Thermoelectric generation technology is a technology of utilizing the Sai Beike of semi-conductor thermoelectric material (Seebeck) effect and Peltier (Peltier) effect that heat energy and electric energy are directly changed, comprises thermoelectric power generation and thermoelectric cooling dual mode.Utilize the Seebeck effect can be used for generating electricity, utilize the Peltier effect then can realize refrigeration or temperature control.Said material is with a wide range of applications in generating and refrigerating field, and TRT has advantages such as volume is little, noiselessness, no wearing and tearing, good reliability, life-span length.Bi 2Te 3(bismuth telluride) based semiconductor is near one of thermoelectric material that best performance is got over the current room temperature, is applicable to aspects such as industrial waste heat generating, automobile exhaust gas generating.The quality of the thermoelectricity capability of thermoelectric material is mainly characterized by thermoelectric figure of merit Z: Z defines with following formula:
Z＝S 2σ/κ
In the formula,
S: Seebeck coefficient (V/K)
σ: resistivity (S/m)
κ: thermal conductivity (W/Km)
Hence one can see that, and in order to improve the performance of thermoelectric material, effective method is to increase Seebeck coefficient and conductivity, reduces thermal conductivity.The emphasis of current thermoelectric material research field and difficult point are to prepare the Bi with high-performance and high-mechanical property 2Te 3Pyroelectric material.At Bi 2Te 3In the thermoelectric material of matrix, P-type Bi 0.5Sb 1.5Te 3Has very important researching value.Adopt the method for MA (mechanical alloying) to prepare P-type Bi 0.5Sb 1.5Te 3The thermoelectric material powder; Utilize the mechanical energy that the ball mill high speed rotating is produced in the ma process to make material powder under solid phase, realize alloying; Avoid the volatilization problem of element such as Bi, Te under the molten condition; Can prepared composition evenly, organize tiny material, particles of powder Du Keda nanoscale.Being evenly distributed with of composition is beneficial to the minimizing alloy scattering, improve conductivity, and tiny crystallite dimension increased the scattering of low frequency phonon, can reduce the thermal conductivity of material, thereby improved its thermoelectricity capability.The P-type nanometer Bi that mechanical alloying makes 0.5Sb 1.5Te 3The thermoelectric material powder adopts vacuum heating-press sintering to prepare block materials.Heat pressing process comprises parameters such as sintering temperature, pressure, atmosphere, programming rate, temperature retention time.Adopt different sintering temperatures can significantly change the thermal conductivity and the conductivity of material.Generally speaking, temperature is high more, pressure is big more, and the sample grain growth after the sintering is abundant, and density is better, possesses better thermoelectricity capability.In sintering process, introduce inert gas, can reduce the oxidation of material.
From present research, adopt mechanical alloying and very fast hot-pressing sintering method preparation to have the P-type Bi of nano-scale particle 0.5Sb 1.5Te 3Thermoelectric material does not also appear in the newspapers.The present invention adopts the prepared by mechanical alloy nanometer powder, prepares the tiny P-type Bi of crystal grain in conjunction with the vacuum heating-press sintering method 0.5Sb 1.5Te 3The thermoelectric material block.Reduce the thermal conductivity of material through crystal grain thinning, finally improve P-type Bi 0.5Sb 1.5Te 3The thermoelectricity capability of thermoelectric material.
Summary of the invention
The purpose of this invention is to provide a kind of use mechanical alloying combines the vacuum heating-press sintering method to prepare P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material is through improving the thermoelectricity capability of material to preparation technology's design and control.
The present invention is a raw material with high-purity (99.99%) Bi powder, Sb powder and Te powder, is combined to Bi through mechanical alloy 0.5Sb 1.5Te 3The compound nano powder utilizes the vacuum heating-press sintering method with Bi 0.5Sb 1.5Te 3Forerunner's nanometer powder sinters fine and close thin crystal block body heat electric material into.The technical scheme that the present invention adopted is: adopt the thin brilliant Bi of mechanical alloying (MA) and vacuum heating-press sintering (HP) preparation 0.5Sb 1.5Te 3The technology of thermoelectric material.
The present invention is achieved through following technical scheme.
A kind of P type nanostructure Bi 0.5Sb 1.5Te 3The preparation method of block thermoelectric material has following steps:
(1) be initial feed with simple substance Bi powder, Sb powder and Te powder, press Bi: Sb: Te=0.5: 1.5: 3 atomic ratio batchings, with three kinds of powder, ball milling in high energy ball mill; Use stainless steel jar mill and abrading-ball, the mass ratio of ball material is 20: 1, adds alcohol in the ball grinder as ball-milling medium, and the amount that adds alcohol was not advisable there not to be powder and abrading-ball, feeds argon gas in the ball grinder and protects; Wherein, batching, tinning and sampling are all carried out in vacuum glove box; This process obtains the P type Bi of nanostructure through the method for mechanical alloying 0.5Sb 1.5Te 3The thermoelectric material powder;
(2) powder of the mechanical alloying of step (1) is dried in drying box, bake out temperature is 50 ℃～120 ℃, and drying time is 5～10h, then, powder is placed alcohol, carries out ultrasonic dispersion 3h;
(3) with the P type Bi after the ultrasonic dispersion of step (2) 0.5Sb 1.5Te 3The thermoelectric material powder graphite jig of packing into places the vacuum heating-press sintering stove with graphite jig then, and programming rate is 10 ℃/min; Sintering temperature is 400～500 ℃; Sintering pressure is 100～150MPa, and heat-insulation pressure keeping time 2h, vacuum heating-press sintering make P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material.
Simple substance Bi powder, Sb powder and the Te powder of said step (1) initial feed are the high pure raw material of purity 99.99%;
The alcohol purity of said step (1), (2) is 99.7%.
The ball milling speed of said step (1) is 450r/min; The ball milling time is 60h.
The powder that the mechanical alloying of said step (2) obtains at 40KHz, carried out ultrasonic dispersion 3h under the 100W power before very fast hot pressing.
The vacuum hotpressing temperature of said step (3) is 500 ℃, and vacuum hotpressing pressure is 150MPa, and the vacuum hotpressing heat-insulation pressure keeping time is 2h.
The invention has the beneficial effects as follows, the P type nanostructure Bi with nano-scale particle of a kind of employing mechanical alloying (MA) and vacuum heating-press sintering (HP) method preparation is provided 0.5Sb 1.5Te 3Block thermoelectric material.Compared with prior art; Utilize the mechanical energy that the ball mill high speed rotating is produced in the ma process to make material powder under solid phase, realize alloying; Avoided the volatilization problem of elements such as Bi, Sb, Te under the molten condition, can prepare composition evenly, organize tiny material.The particles of powder degree has reached nanoscale, has effectively increased phon scattering, has reduced thermal conductivity, and then has improved thermoelectricity capability.
Description of drawings
Fig. 1 is the Bi of mechanical ball milling 60h 0.5Sb 1.5Te 3The X-ray diffractogram of powder;
Fig. 2 is the Bi of mechanical ball milling 60h 0.5Sb 1.5Te 3The microstructure pattern of powder;
Fig. 3 is 400 ℃ of hot pressing temperatures, pressure 100MPa, the P type Bi of heat-insulation pressure keeping time 2h 0.5Sb 1.5Te 3The microstructure pattern of block thermoelectric material;
Fig. 4 is 450 ℃ of hot pressing temperatures, pressure 100MPa, the P type Bi of heat-insulation pressure keeping time 2h 0.5Sb 1.5Te 3The microstructure pattern of block thermoelectric material;
Fig. 5 is 500 ℃ of hot pressing temperatures, pressure 150MPa, the P type Bi of heat-insulation pressure keeping time 2h 0.5Sb 1.5Te 3The microstructure pattern of block thermoelectric material;
Fig. 6 is the conductivity variations under the different hot compression parameterses;
Fig. 7 is that the Seebeck under the different hot compression parameterses changes;
Fig. 8 is that the thermal conductivity under the different hot compression parameterses changes;
Fig. 9 is that the power factor under the different hot compression parameterses changes;
Figure 10 is that the Z value under the different hot compression parameterses changes.
Embodiment
It is that 99.99% chemical pure is a raw material that the present invention adopts commercially available purity, and specific embodiment is following.
Embodiment 1
(400 ℃ of hot pressing temperatures, pressure 100MPa, the preparation of the hot pressed sintering sample of heat-insulation pressure keeping time 2h)
(1) high-purity Bi, Sb, Te simple substance powder are pressed Bi: Sb: Te=0.5: 1.5: 3 atomic ratios batching, with the mixed-powder ball grinder of packing into, and add purity be 99.7% alcohol as ball-milling medium, batching, tinning and sampling are all carried out in vacuum glove box.Ball milling is accomplished on high energy ball mill, uses stainless steel jar mill and abrading-ball, in order to prevent the powder oxidation in the MA process; Feeding the inert gas argon gas protects; Ratio of grinding media to material was selected for use 20: 1, and the amount that adds alcohol was not advisable there not to be powder and abrading-ball, and rotational speed of ball-mill is 450rpm; The ball milling time is 60h, obtains the Bi of complete alloying 0.5Sb 1.5Te 3Powder (Fig. 1), its crystallite dimension can reach tens nanometers (Fig. 2).Place drying box to dry in the powder of complete mechanical alloying, bake out temperature is 90 ℃, and drying time is 8h, then, powder is placed alcohol, adopts 40KHz, and the power of 100W carries out ultrasonic dispersion 3h.
(2) the nanoscale Bi that adopts ultrasonic dispersion to obtain 0.5Sb 1.5Te 3Powder in its graphite jig of packing into, puts it in the vacuum heating-press sintering stove then, adopts the vacuum heating-press sintering legal system to be equipped with P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material.The hot pressed sintering condition is: hot pressing temperature is 400 ℃, and programming rate is 10 ℃/min, and pressure is 100Mpa, and temperature retention time is 2h, and vacuum heating-press sintering obtains the Bi of P type nanostructure 0.5Sb 1.5Te 3Block thermoelectric material carries out SEM to its section and observes (Fig. 3).
The Bi of the P type nanostructure that (3) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into 3 * 3 * 15mm after with sand papering, carries out the test of material electrical property, and content measurement comprises conductivity of electrolyte materials σ (S/m) (Fig. 6), and Seebeck coefficient S (V/K) (Fig. 7).
The Bi of the P type nanostructure that (4) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into after with sand papering Carry out the test (Fig. 8) of material thermal conductivity κ (W/Km).
(5) according to the data that record, according to thermoelectric figure of merit formula Z=S 2The thermoelectricity capability of σ/κ evaluating material.Experimental result shows, the Bi of the P type nanostructure of present embodiment preparation 0.5Sb 1.5Te 3The power factor of thermoelectric material is up to 0.0008 (Fig. 9), and thermoelectric figure of merit Z reaches 0.002 (Figure 10).
Embodiment 2
(500 ℃ of hot pressing temperatures, pressure 100MPa, the preparation of the hot pressed sintering sample of heat-insulation pressure keeping time 2h)
(1) high-purity Bi, Sb, Te simple substance powder are pressed Bi: Sb: Te=0.5: 1.5: 3 atomic ratios batching, with the mixed-powder ball grinder of packing into, and add purity be 99.7% alcohol as ball-milling medium, batching, tinning and sampling are all carried out in vacuum glove box.Ball milling is accomplished on high energy ball mill, uses stainless steel jar mill and abrading-ball, in order to prevent the powder oxidation in the MA process; Feeding the inert gas argon gas protects; Ratio of grinding media to material was selected for use 20: 1, and the amount that adds alcohol was not advisable there not to be powder and abrading-ball, and rotational speed of ball-mill is 450rpm; The ball milling time is 60h, obtains the Bi of complete alloying 0.5Sb 1.5Te 3Powder (Fig. 1), its crystallite dimension can reach tens nanometers (Fig. 2).Place drying box to dry in the powder of complete mechanical alloying, bake out temperature is 90 ℃, and drying time is 8h, then, powder is placed alcohol, adopts 40KHz, and the power of 100W carries out ultrasonic dispersion 3h.
(2) the nanoscale Bi that adopts ultrasonic dispersion to obtain 0.5Sb 1.5Te 3Powder in its graphite jig of packing into, puts it in the vacuum heating-press sintering stove then, adopts the vacuum heating-press sintering legal system to be equipped with P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material.The hot pressed sintering condition is: the temperature of hot pressing is 500 ℃, and programming rate is 10 ℃/min, and pressure is 100Mpa, and temperature retention time is 2h, and vacuum heating-press sintering obtains the Bi of P type nanostructure 0.5Sb 1.5Te 3Block thermoelectric material carries out SEM to its section and observes (Fig. 4).
The Bi of the P type nanostructure that (3) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into 3 * 3 * 15mm after with sand papering, carries out the test of material electrical property, and content measurement comprises conductivity of electrolyte materials σ (S/m) (Fig. 6), and Seebeck coefficient S (V/K) (Fig. 7).
The Bi of the P type nanostructure that (4) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into after with sand papering
Figure BDA00001705297400042
Carry out the test (Fig. 8) of material thermal conductivity κ (W/Km).
(5) according to the data that record, according to thermoelectric figure of merit formula Z=S 2The thermoelectricity capability of σ/κ evaluating material.Experimental result shows, the Bi of the P type nanostructure of this method preparation 0.5Sb 1.5Te 3The power factor of thermoelectric material is brought up to 0.0009 (Fig. 9), and thermoelectric figure of merit Z is improved to some extent than embodiment 1, and maximum still remains on about 0.002 (Figure 10).
Embodiment 3
(550 ℃ of hot pressing temperatures, pressure 150MPa, the preparation of the hot pressed sintering sample of heat-insulation pressure keeping time 2h)
(1) high-purity Bi, Sb, Te simple substance powder are pressed Bi: Sb: Te=0.5: 1.5: 3 atomic ratios batching, with the mixed-powder ball grinder of packing into, and add purity be 99.7% alcohol as ball-milling medium, batching, tinning and sampling are all carried out in vacuum glove box.Ball milling is accomplished on high energy ball mill, uses stainless steel jar mill and abrading-ball, in order to prevent the powder oxidation in the MA process; Feeding the inert gas argon gas protects; Ratio of grinding media to material was selected for use 20: 1, and the amount that adds alcohol was not advisable there not to be powder and abrading-ball, and rotational speed of ball-mill is 450rpm; The ball milling time is 60h, obtains the Bi of complete alloying 0.5Sb 1.5Te 3Powder (Fig. 1), its crystallite dimension can reach tens nanometers (Fig. 2).Place drying box to dry in the powder of complete mechanical alloying, bake out temperature is 90 ℃, and drying time is 8h, then, powder is placed alcohol, adopts 40KHz, and the power of 100W carries out ultrasonic dispersion 3h.
(2) the nanoscale Bi that adopts ultrasonic dispersion to obtain 0.5Sb 1.5Te 3Powder in its graphite jig of packing into, puts it in the vacuum heating-press sintering stove then, adopts the vacuum heating-press sintering legal system to be equipped with P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material.The hot pressed sintering condition is: the temperature of hot pressing is 500 ℃, and programming rate is 10 ℃/min, and pressure is 150Mpa, and temperature retention time is 2h, and vacuum heating-press sintering obtains the Bi of P type nanostructure 0.5Sb 1.5Te 3Block thermoelectric material carries out SEM to its section and observes (Fig. 5).
The Bi of the P type nanostructure that (3) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into 3 * 3 * 15mm after with sand papering, carries out the test of material electrical property, and content measurement comprises conductivity of electrolyte materials σ (S/m), and (Fig. 6), Seebeck coefficient S (V/K) (Fig. 7).
The Bi of the P type nanostructure that (4) obtains through the vacuum heating-press sintering method 0.5Sb 1.5Te 3The block thermoelectric material sample is cut into after with sand papering
Figure BDA00001705297400051
Carry out the test (Fig. 8) of material thermal conductivity κ (W/Km).
(5) according to the data that record, according to thermoelectric figure of merit formula Z=S 2The thermoelectricity capability of σ/κ evaluating material.Experimental result shows, the Bi of the P type nanostructure of this method preparation 0.5Sb 1.5Te 3The power factor of thermoelectric material is up to 0.001 (Fig. 9), and thermoelectric figure of merit Z reaches 0.0023 (Figure 10).

Claims (6)

1. P type nanostructure Bi 0.5Sb 1.5Te 3The preparation method of block thermoelectric material has following steps:
(1) be initial feed with simple substance Bi powder, Sb powder and Te powder, press Bi: Sb: Te=0.5: 1.5: 3 atomic ratio batchings, with three kinds of powder, ball milling in high energy ball mill; Use stainless steel jar mill and abrading-ball, the mass ratio of ball material is 20: 1, adds alcohol in the ball grinder as ball-milling medium, and the amount that adds alcohol was not advisable there not to be powder and abrading-ball, feeds argon gas in the ball grinder and protects; Wherein, batching, tinning and sampling are all carried out in vacuum glove box; This process obtains the P type Bi of nanostructure through the method for mechanical alloying 0.5Sb 1.5Te 3The thermoelectric material powder;
(2) powder of the mechanical alloying of step (1) is dried in drying box, bake out temperature is 50 ℃～120 ℃, and drying time is 5～10h, then, powder is placed alcohol, carries out ultrasonic dispersion 3h;
(3) with the P type Bi after the ultrasonic dispersion of step (2) 0.5Sb 1.5Te 3The thermoelectric material powder graphite jig of packing into places the vacuum heating-press sintering stove with graphite jig then, and programming rate is 10 ℃/min; Sintering temperature is 400～500 ℃; Sintering pressure is 100～150MPa, and heat-insulation pressure keeping time 2h, vacuum heating-press sintering make P type nanostructure Bi 0.5Sb 1.5Te 3Block thermoelectric material.
2. according to a kind of P type nanostructure Bi of claim 1 0.5Sb 1.5Te 3The preparation method of block thermoelectric material is characterized in that, simple substance Bi powder, Sb powder and the Te powder of said step (1) initial feed are the high pure raw material of purity 99.99%.
3. according to a kind of P type nanostructure Bi of claim 1 0.5Sb 1.5Te 3The preparation method of block thermoelectric material is characterized in that, the alcohol purity of said step (1), (2) is 99.7%.
4. according to a kind of P type nanostructure Bi of claim 1 0.5Sb 1.5Te 3The preparation method of block thermoelectric material is characterized in that, the ball milling speed of said step (1) is 450r/min; The ball milling time is 60h.
5. according to a kind of P type nanostructure Bi of claim 1 0.5Sb 1.5Te 3The preparation method of block thermoelectric material is characterized in that, the powder that the mechanical alloying of said step (2) obtains at 40KHz, carried out ultrasonic dispersion 3h under the 100W power before very fast hot pressing.
6. according to a kind of P type nanostructure Bi of claim 1 0.5Sb 1.5Te 3The preparation method of block thermoelectric material, the vacuum hotpressing temperature that it is characterized in that said step (3) is 500 ℃, and vacuum hotpressing pressure is 150MPa, and the vacuum hotpressing heat-insulation pressure keeping time is 2h.
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CN108103336A (en) * 2016-11-25 2018-06-01 河南城建学院 Bi1-xSbxThermoelectric material and preparation method thereof
CN109004079A (en) * 2018-07-30 2018-12-14 哈尔滨师范大学 The preparation method of p-type Y doping pseudo-ternary thermoelectric materials
WO2019127174A1 (en) * 2017-12-28 2019-07-04 中国科学院物理研究所 Hot-press sintering apparatus, block thermoelectric material of micro-nano porous structure, and manufacturing method therefor
CN110818415A (en) * 2019-09-29 2020-02-21 中机第一设计研究院有限公司 Regulation and control P type Bi2Te3Method for texture and orientation of base materials
CN112768594A (en) * 2021-01-11 2021-05-07 中国科学技术大学 Bismuth-tellurium series natural superlattice thermoelectric material and preparation method thereof
CN114249304A (en) * 2020-09-25 2022-03-29 中国科学院大连化学物理研究所 High-performance BiTe-based composite thermoelectric material and preparation method thereof
CN115466119A (en) * 2022-09-22 2022-12-13 广西自贸区见炬科技有限公司 BiSbTe-based nano composite material with high ZT value, and preparation method and application thereof
CN116693292A (en) * 2023-06-06 2023-09-05 西安交通大学 p-type Bi 2 Te 3 Method for preparing base thermoelectric material

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CN108103336B (en) * 2016-11-25 2019-06-28 河南城建学院 Bi1-xSbxThermoelectric material and preparation method thereof
CN108103336A (en) * 2016-11-25 2018-06-01 河南城建学院 Bi1-xSbxThermoelectric material and preparation method thereof
CN107681043B (en) * 2017-09-15 2020-04-21 武汉理工大学 Bismuth telluride-based composite thermoelectric material of flexible thermoelectric device and preparation method thereof
CN107681043A (en) * 2017-09-15 2018-02-09 武汉理工大学 A kind of bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application and preparation method thereof
WO2019127174A1 (en) * 2017-12-28 2019-07-04 中国科学院物理研究所 Hot-press sintering apparatus, block thermoelectric material of micro-nano porous structure, and manufacturing method therefor
CN109004079A (en) * 2018-07-30 2018-12-14 哈尔滨师范大学 The preparation method of p-type Y doping pseudo-ternary thermoelectric materials
CN109004079B (en) * 2018-07-30 2023-03-28 哈尔滨师范大学 Preparation method of P-type Y-doped pseudo-ternary thermoelectric material
CN110818415A (en) * 2019-09-29 2020-02-21 中机第一设计研究院有限公司 Regulation and control P type Bi2Te3Method for texture and orientation of base materials
CN114249304A (en) * 2020-09-25 2022-03-29 中国科学院大连化学物理研究所 High-performance BiTe-based composite thermoelectric material and preparation method thereof
CN112768594A (en) * 2021-01-11 2021-05-07 中国科学技术大学 Bismuth-tellurium series natural superlattice thermoelectric material and preparation method thereof
CN112768594B (en) * 2021-01-11 2024-04-02 中国科学技术大学 Bismuth-tellurium natural superlattice thermoelectric material and preparation method thereof
CN115466119A (en) * 2022-09-22 2022-12-13 广西自贸区见炬科技有限公司 BiSbTe-based nano composite material with high ZT value, and preparation method and application thereof
CN116693292A (en) * 2023-06-06 2023-09-05 西安交通大学 p-type Bi 2 Te 3 Method for preparing base thermoelectric material

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