CN1962416A - Preparation process of bismuth telluride base thermoelectrical material - Google Patents
Preparation process of bismuth telluride base thermoelectrical material Download PDFInfo
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Abstract
The invention discloses a preparing method of thermoelectric material of bismuth telluride base through regional fusing growing and thermoelectric combined method, which is characterized by the following: grinding crystal; sieving; obtaining original powder material with certain grain size distribution; sintering in the thermoelectric furnace; preparing block material with excellent grain orientation and mechanical property through thermoelectric method.
Description
Technical field
The present invention relates to thermoelectric material, specifically a kind of Tellurobismuthite (Bi that has good mechanical property and thermoelectricity capability simultaneously
2Te
3) preparation technology of base thermoelectricity material.
Background technology
Thermo-electric conversion is that Seebeck (Seebeck) effect and Pa Er card (Peltier) effect of utilizing semiconductor material realize the technology that heat energy and electric energy are directly changed mutually, and its efficiency of conversion depends primarily on the zero dimension performance index of material, i.e. ZT value (ZT=α
2σ T/ κ is that Seebeck coefficient, σ are that specific conductivity, κ are that thermal conductivity, T are absolute temperature for α wherein).The principal element that the restriction thermoelectric material is used is that efficiency of conversion is lower; Yet along with environment and energy problem protrude day by day, especially people notice the environmental problem that freon refrigerant brings in the late nineteen eighties in last century, make the advantage of thermo-electric device receive publicity again.Thermoelectric conversion system has little, the characteristics such as exhaust emission material not of no drive disk assembly, noiselessness, system bulk, is with a wide range of applications.The bismuth telluride-base alloy is since being found the 1950's, be still near one of thermoelectric material of performance the best room temperature so far, its ZT value is about 1.0, the part refrigeration and the high-precision temperature control of electronic devices and components such as laser diode, CCD, infrared eye have been widely used in states such as Japan, America and Europes, the thermoelectric refrigeration The Application of Technology is military and also expansion day by day of civil area at some other, especially be not the application scenario of major consideration with the efficiency of conversion a lot, thermo-electric device has incomparable advantage especially.
The crystalline structure of Tellurobismuthite belongs to trigonal system, can be considered the hexahedron laminate structure along crystalline C direction of principal axis, and its thermoelectricity capability is very strong anisotropy, has the maximum performance figure of merit on the direction that is parallel to basal plane (00l).Therefore, usually adopt the method for crystal growth, as zone melting method or Bridgman method to obtain to have the bismuth telluride-base crystalline material of good dies orientation, yet the material that is obtained causes physical strength low along the basal plane cleavage easily, thereby greatly reduces the utilization ratio of material and the work reliability of components and parts.Current, be target with high strength and high thermoelectricity capability, be to seek novel fabricating technology at the research emphasis of bismuth telluride-base thermoelectric material.Adopt mechanical alloying can effectively eliminate existing component segregation phenomenon in the crystal growing process, and avoided the volatilization problem of low melting point element such as Bi, Te under the molten state, finally can obtain evenly tiny microtexture; But it is comparatively serious to cause powder to pollute in mechanical milling process, and preparation cycle is long.In addition, after this adopt the prepared block materials of method such as hot pressing, hot extrusion,, do not make thermoelectricity capability not satisfactory owing to the grain orientation degree is high though mechanical property makes moderate progress.
The maximum characteristics of bismuth telluride-base thermoelectric material are that thermoelectricity capability is an anisotropy, therefore need to consider the grain orientation of material in preparation process.The inventor once adopted and will distinguish molten crystal pulverizing, then in conjunction with discharge plasma sintering (SPS) technology, obtained to have the block materials of desirable mechanical property, and the molten crystal in the district of thermoelectricity capability and same composition is suitable, this invention is documented in the Chinese patent that is called " a kind of preparation method of bismuth telluride-base thermoelectric material " (notification number 1230377, December 7 2005 day for announcing).Discharge plasma sintering (SPS) is a kind of novel material preparation technology, its principal feature is to utilize pulsed current direct heating and surface active, realize the quick densifying sintering of material, the uniform crystal particles of the sintered specimen that obtains, density height, mechanical property are good.The principal feature of discharge plasma sintering (SPS) is to utilize pulsed current direct heating and surface active, realizes the quick densifying sintering of material.In preparation process, electric current directly passes through mould and sample, and sample itself and mould are generated heat together, so heat-up rate can be very fast, even can reach 600K/ minute.But the deadly defect of discharge plasma sintering (SPS) is exactly that equipment cost is too high, and production capacity is difficult to practical requirement, and the discharge plasma sintering stove is few in number at home, at present only for research unit adopts, so with industrialization suitable distance is arranged.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation technology of new bismuth telluride-base thermoelectric material is provided, this preparation technology does not adopt expensive discharge plasma sintering (SPS) equipment, reaches the Tellurobismuthite (Bi that preparation has good dies orientation and mechanical property equally
2Te
3) purpose of base thermoelectricity material.This preparation process is simple, and equipment cost is low, has good industrial prospect.
The present invention is based on the growing by zone melting crystalline material, at first it is pulverized and sieve, to obtain the having initial powder body material that certain particle size distributes, utilize pressure sintering to prepare corresponding block materials then, purpose is to explore the fabricating technology that is fit to actual production, to obtain to have simultaneously the Tellurobismuthite (Bi of good mechanical property and thermoelectricity capability
2Te
3) base thermoelectricity material.Based on the growing by zone melting crystal, can guarantee that the crystal grain of material has good orientation, this is the basis that obtains to have good thermoelectricity capability.Every processing parameter by the control pressure sintering adopts relatively low sintering temperature and soaking time, can make preparation cycle reasonable, can suppress the volatilization of Tellurobismuthite low melting point element simultaneously, thereby can well control the chemical constitution of agglomerated material; Compare with the molten crystal in district, its mechanical property increases substantially, and thermoelectricity capability remains unchanged substantially.The present invention adopts growing by zone melting linkage heat platen press, and preparation process is simple, and preparation facilities is cheap, and the utilization ratio of prepared material has obtained to significantly improve, and has greatly improved the stability and the reliability of thermo-electric device simultaneously.
One of key problem in technology of the present invention is to distinguish the pulverizing and the classification of melting crystalline material and sieves, and distributes to obtain certain particle, and this is to guarantee that material has the important foundation of desirable microstructure (grain orientation).Two of key problem in technology is the optimization of sintering process parameter, the pattern of mainly comprise sintering temperature, exerting pressure and size, heat-up rate, soaking time, the type of cooling etc., thereby make the sintering block materials have good grain orientation, and by regulating the stoicheiometry and the carrier concentration of material, final acquisition has the block materials of good mechanical property and thermoelectricity capability simultaneously.Following each step is specifically arranged:
1, the preparation of the molten crystalline material in district
This is the basis that obtains to have good product grain orientation, is the key that guarantees conducting material thermoelectricity performance.With element powders such as commercial Bi, Sb, Te, Se is raw material, is that doping agent is to regulate the carrier concentration to 10 of material with corresponding chemical feedstocks
25/ m
3Magnitude, thus make it have the ideal thermoelectricity capability; By adopting processing parameters such as rational melt temperature, melting zone width, thermograde, the speed of growth, utilize zone melting method to prepare Tellurobismuthite (Bi
2Te
3) basic crystalline material.Usually the melt temperature of taking is 700～800 ℃; Heat-up rate is 25 ℃/min; The melting zone width is 30～40mm; Thermograde is 25～50 ℃/cm; The speed of growth is 25～30mm/h.According to different stoicheiometries, prepare N type Bi
2(Te, Se)
3With the P type (Bi, Sb)
2Te
3Base thermoelectricity material.
2, the preparation of powder body material and pre-treatment
To melting the crystalline material pulverizing and sieve in the district that is obtained, to obtain the initial powder body material that different grain size distributes.At first will distinguish molten crystal and place certain density hydrofluoric acid solution to soak, and take out the back with alcohol and washed with de-ionized water, be about 7 until its surperficial pH value, carries out drying at last in a vacuum; Perhaps directly take the mode of mechanical grinding, to remove the oxide impurity layer on surface.Adopt Steel Vessel as the pulverizing instrument, crushing process can carry out in glove box, and introduces protection of inert gas such as argon gas.In atmosphere of inert gases, utilize the standard sub-sieve that powder is sieved, to control its size-grade distribution.Operate in air if pulverize, then need powder to be carried out aftertreatment, (Ar+5～40%H in reducing atmosphere with the process of sieving
2) be heated to about 300 ℃, and be incubated about 4 hours, the problem of oxidation of being introduced to avoid in the preparation process.Before sintering, powder is carried out ultrasonic pretreatment, make sintering powder in mould, form certain distribution of orientations.
3, pressure sintering
Pressure sintering mainly is to utilize burner hearth heating element all around to mould and sample radiation heating, and this process needs carry out in vacuum condition or inert atmosphere, can select graphite or special steel die for use.In preparation process, need strict control process parameters, the pattern of mainly comprise sintering temperature, exerting pressure and size, heat-up rate, soaking time, the type of cooling etc.Wherein, sintering temperature and temperature rise rate are regulated by the size of received current and voltage.Sintering range is 350～550 ℃; The heat-up rate scope is 10～100 ℃/min; How many definite concrete soaking times according to material are generally 5～120min; Can take substep pressurization, in initial stage of sintering or disposable pressurization isotype of insulation initial stage, institute's applied pressure scope is 20～120MPa; Can take modes such as naturally cooling or the quick cooling of feeding rare gas element at last.
The sign of material mainly comprises the orientation analysis of crystal grain, every thermoelectricity capability parameter, bending strength and the device maximum temperature difference Δ T that obtain such as Seebeck coefficient α, conductivity, thermal conductivity κ
mMeasurement.Find according to X-ray diffraction (XRD) and scanning electron microscope (SEM), utilize growing by zone melting linkage heat platen press, the crystal grain of the block materials that obtains is good orientation, as shown in Figure 1, is very strong (00l) high preferred orientation perpendicular to the direction of being exerted pressure in the preparation process.The ZT value of each agglomerated material is about 0.9～1.1; Utilize the maximum temperature difference Δ T of the prepared device of sintering block materials
mBe 64～67 ℃, and utilize the molten prepared device maximum temperature difference of crystalline material of respective area to be about 67 ℃.The molten crystalline bending strength in district only is about 10MPa, and the significantly improving to the 80MPa of sintering block materials.
With the component is 15%Bi
2Te
3-85%Sb
2Te
3The P-type material of+3wt%Te is an example, shown in Fig. 2-4: compare with the molten crystal in district, through after the hot pressed sintering, conductivity of electrolyte materials σ decreases, but Seebeck coefficient α increases and thermal conductivity κ reduces, and finally is embodied in performance figure of merit ZT what for to being better than the molten crystalline material in corresponding district.
Technical scheme of the present invention is:
A kind of preparation technology of bismuth telluride-base thermoelectric material is characterized in that: Tellurobismuthite matrix component is Bi
2Te
3-Bi
2Se
3N type material or matrix component be Bi
2Te
3-Sb
2Te
3P-type material;
Preparation technology may further comprise the steps:
(1) utilize zone melting method to prepare Tellurobismuthite (Bi
2Te
3) basic crystalline material, the melt temperature of taking is 700～800 ℃, and heat-up rate is 25 ℃/min, and the melting zone width is 30～40mm, and thermograde is 25～50 ℃/cm, the speed of growth is 25～30mm/h;
(2) will distinguishing molten crystalline material, to place concentration be that 10～15% hydrofluoric acid solution soaks 30min, takes out the back with alcohol and washed with de-ionized water, is 7 until its surperficial pH value, and dry in a vacuum; Perhaps directly take the mode of mechanical grinding, to remove the oxide impurity layer on surface;
(3) adopt Steel Vessel to pulverize distinguishing molten crystalline material as the pulverizing instrument;
(4) utilize the standard sub-sieve that powder is sieved, make initial powder form different size-grade distribution, choosing powder that initial particle size is 180～380 μ m or the powder of 120～180 μ m or the powder of 96～120 μ m is that raw material carries out hot pressed sintering; Pulverize and the process of sieving is carried out in air, perhaps adopt the argon gas protection,, then need pulverizing and the powder after sieving carries out aftertreatment, promptly containing 20%H if in air, pulverize and sieve operation
2Ar gas atmosphere under, with pulverize and sieve after powder be heated to 320 ℃ and be incubated 4 hours;
(5) powder is packed into carry out ultrasonic vibration behind graphite jig or the steel die and handle;
(6) in hot pressing furnace powder is carried out sintering, the hot pressing preparation process is carried out at vacuum condition or under inert atmosphere, and the sintering temperature of employing is 350～550 ℃, and temperature rise rate is 10～100 ℃/min, and soaking time is 5～120min; Adopt two step pressing mode, promptly institute's applied pressure is 20～50MPa before the sintering, and holding stage institute applied pressure is 80～120MPa; Perhaps adopting pressing mode one time, is 60～80Mpa disposable the exerting pressure of initial stage of sintering promptly;
(7) take naturally cooling or feeding rare gas element to cool off fast.
The invention provides the technology that a kind of growing by zone melting linkage heat platen press prepares bismuth telluride-base thermoelectric material, by the Tellurobismuthite (Bi of its preparation
2Te
3) base thermoelectricity material has good grain orientation and mechanical property.This technology is grain orientation by the microstructure of control material, has improved its mechanical property on the basis of maintenance heat electrical property significantly, and the stability of utilization ratio, workability and components and parts of material and reliability etc. all are greatly improved.This technology devices needed cost is low, and with regard to equipment price, the hot-press equipment of identical production capacity is 1/10th of a SPS equipment, and preparation process is simple, thereby has good industrial prospect.
Description of drawings
Fig. 1 is the X-ray diffractogram of hot pressing block materials perpendicular to the surface of exerting pressure;
Fig. 2 is for distinguishing molten crystal and hot pressing block conductivity of electrolyte materials σ with measuring the variation of temperature graph of a relation;
Fig. 3 melts the thermal conductivity κ of crystal and hot pressing block materials with measuring the variation of temperature graph of a relation for the district;
Fig. 4 melts the performance figure of merit ZT of crystal and hot pressing block materials with measuring the variation of temperature graph of a relation for the district.
Embodiment
Below the present invention is described in further detail.
Embodiment 1:
Matrix component is 93%Bi
2Te
3-7%Bi
2Se
3N type material:
At first will distinguishing molten crystalline material, to place concentration be that 10～15% hydrofluoric acid solution soaks 30min, takes out the back with alcohol and washed with de-ionized water, and dry in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process adopts protection of inert gas such as argon gas.Utilize the standard sub-sieve that powder is sieved, make initial powder form different size-grade distribution, the powder of choosing 180～380 μ m is that raw material carries out hot pressed sintering.Powder is packed into behind the graphite jig, at first carry out ultrasonic vibration and handle, to form certain distribution of orientations.The hot pressing preparation process is carried out under vacuum condition, and the sintering temperature of employing is 460 ℃; Temperature rise rate is 50 ℃/min; Soaking time is 20min; Adopt two step pressing mode, promptly institute's applied pressure is 40MPa before the sintering, and holding stage institute applied pressure is 80MPa.Take out near at last sample being naturally cooled to room temperature.
The bending strength of the hot pressing block materials that obtains is 75MPa; Thermoelectricity capability figure of merit Z is 3.2 * 10
-3/ K.
Embodiment 2:
Matrix component is 26%Bi
2Te
3-74%Sb
2Te
3P-type material:
At first adopt the mode of mechanical grinding, to remove the thin oxide layer on molten crystalline material surface, district.Adopt Steel Vessel as the pulverizing instrument, and utilize the standard sub-sieve that powder is sieved, pulverize and the process of sieving is all operated in air, at last (Ar+5～40%H in reducing atmosphere
2) be heated to 320 ℃ and be incubated 6 hours.The powder of choosing 180～380 μ m is that raw material carries out hot pressed sintering.With the steel die that it is special that powder is packed into, under vacuum condition, carry out hot pressing, the sintering temperature that is adopted is 420 ℃; Temperature rise rate is 40 ℃/min; Soaking time is 20min; Adopt two step pressing mode, institute's applied pressure is 50MPa before the sintering, and holding stage institute applied pressure is 100MPa.Take out near at last sample being naturally cooled to room temperature.
The bending strength of the hot pressing block materials that obtains is 70MPa; Thermoelectricity capability figure of merit Z is 3.5 * 10
-3/ K.The n type material that is obtained in P-type material that is obtained in this example and the example 1 combines refrigeration device, measures maximum temperature difference Δ T
mIt is 67 ℃.
Embodiment 3:
Initial particle size is the powder body material of 120～180 μ m:
To N type Bi
2(Te, Se)
3The molten crystalline material in district is pulverized and sieved: at first will distinguish molten crystal, to place concentration be that 10～15% hydrofluoric acid solution soaks 15min, takes out the back with alcohol and washed with de-ionized water, and drying in a vacuum.Adopt Steel Vessel as the pulverizing instrument, crushing process carries out in air.Utilize the standard sub-sieve that powder is sieved, to obtain the initial powder that desired particle size distributes.Then powder is carried out aftertreatment, (Ar+20%H under reducing atmosphere
2) be heated to 320 ℃ and be incubated 4 hours.Behind the steel die that it is special that powder is packed into, before sintering, carry out ultrasonic vibration and handle, to form certain distribution of orientations.The hot pressing preparation process is carried out under vacuum condition: the sintering temperature of employing is 480 ℃; Temperature rise rate is 60 ℃/min; Soaking time is 30min; At the disposable applied pressure of initial stage of sintering is 80MPa.In hot pressing furnace, feed argon gas at last, make sample be quickly cooled near the taking-up of room temperature.
The bending strength of the hot pressing block materials that obtains is 70MPa; Thermoelectricity capability figure of merit Z is 3.0 * 10
-3/ K.Utilize the P type powder of same particle size distribution to be 62MPa in the bending strength of the following sintered compact that obtains of identical processing condition; Thermoelectricity capability figure of merit Z is 3.3 * 10
-3/ K.Utilize the two to combine refrigeration device, measure maximum temperature difference Δ T
mIt is 65 ℃.
Embodiment 4:
Initial particle size is the powder body material of 96～120 μ m:
To the P type (Bi, Sb)
2Te
3The molten crystalline material in district is pulverized and sieved: at first will distinguish molten crystal, to place concentration be that 10～15% hydrofluoric acid solution soaks 30min, takes out the back with alcohol and washed with de-ionized water, and drying in a vacuum.Adopt Steel Vessel as the pulverizing instrument, utilize the standard sub-sieve that powder is sieved then, to obtain the initial powder that desired particle size distributes.Pulverize and carry out during the process of sieving is under protection of inert gas.Behind the steel die that it is special that powder is packed into, before sintering, carry out ultrasonic vibration and handle, to form certain distribution of orientations.The hot pressing preparation process is carried out under vacuum condition: the sintering temperature of employing is 400 ℃; Temperature rise rate is 40 ℃/min; Soaking time is 30min; At the disposable applied pressure of initial stage of sintering is 60MPa.Take out near at last sample being naturally cooled to room temperature.
The bending strength of the hot pressing block materials that obtains is 75MPa; Thermoelectricity capability figure of merit Z is 3.1 * 10
-3/ K.Utilize the N type powder of same particle size distribution to be 82MPa in the bending strength of the following sintered compact that obtains of identical processing condition; Thermoelectricity capability figure of merit Z is 2.9 * 10
-3/ K.Utilize the two to combine refrigeration device, measure maximum temperature difference Δ T
mIt is 64 ℃.
Claims (1)
1, a kind of preparation technology of bismuth telluride-base thermoelectric material is characterized in that: Tellurobismuthite matrix component is Bi
2Te
3-Bi
2Se
3N type material or matrix component be Bi
2Te
3-Sb
2Te
3P-type material;
Preparation technology may further comprise the steps:
(1) utilize zone melting method to prepare Tellurobismuthite (Bi
2Te
3) basic crystalline material, the melt temperature of taking is 700～800 ℃, and heat-up rate is 25 ℃/min, and the melting zone width is 30～40mm, and thermograde is 25～50/cm, the speed of growth is 25～30mm/h;
(2) will distinguishing molten crystalline material, to place concentration be that 10～15% hydrofluoric acid solution soaks 30min, takes out the back with alcohol and washed with de-ionized water, is 7 until its surperficial pH value, and dry in a vacuum; Perhaps directly take the mode of mechanical grinding, to remove the oxide impurity layer on surface;
(3) adopt Steel Vessel to pulverize distinguishing molten crystalline material as the pulverizing instrument;
(4) utilize the standard sub-sieve that powder is sieved, make initial powder form different size-grade distribution, choosing powder that initial particle size is 180～380 μ m or the powder of 120～180 μ m or the powder of 96～120 μ m is that raw material carries out hot pressed sintering; Pulverize and the process of sieving is carried out in air, perhaps adopt the argon gas protection,, then need pulverizing and the powder after sieving carries out aftertreatment, promptly containing 20%H if in air, pulverize and sieve operation
2Ar gas atmosphere under, with pulverize and sieve after powder be heated to 320 ℃ and be incubated 4 hours;
(5) powder is packed into carry out ultrasonic vibration behind graphite jig or the steel die and handle;
(6) in hot pressing furnace powder is carried out sintering, the hot pressing preparation process is carried out at vacuum condition or under inert atmosphere, and the sintering temperature of employing is 350～550 ℃, and temperature rise rate is 10～100 ℃/min, and soaking time is 5～120min; Adopt two step pressing mode, promptly institute's applied pressure is 20～50MPa before the sintering, and holding stage institute applied pressure is 80～120MPa; Perhaps adopting pressing mode one time, is 60～80Mpa disposable the exerting pressure of initial stage of sintering promptly;
(7) take naturally cooling or feeding rare gas element to cool off fast.
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| CN102154692A (en) * | 2011-02-25 | 2011-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method of In-Se-based thermoelectric material |
| CN103058152A (en) * | 2013-01-16 | 2013-04-24 | 吉林大学 | Non-bismuth-telluride-doped magnetic material and preparation method thereof |
| CN103101887A (en) * | 2013-02-07 | 2013-05-15 | 浙江工业大学 | Bi3Se4 nanobelt and application of Bi3Se4 nanobelt as thermoelectric material |
| CN104393163A (en) * | 2014-10-09 | 2015-03-04 | 广东先导稀材股份有限公司 | Preparation method of bismuth telluride-based thermoelectric material |
| CN104831344A (en) * | 2015-04-29 | 2015-08-12 | 河南鸿昌电子有限公司 | Crystal pulling method of semiconductor crystal bar |
| CN105047809A (en) * | 2015-06-30 | 2015-11-11 | 中国科学院宁波材料技术与工程研究所 | SnSe-based thermoelectric material and preparation method thereof |
| CN109095916A (en) * | 2018-08-14 | 2018-12-28 | 徐州市江苏师范大学激光科技有限公司 | A kind of method that SPS sintering prepares YAG crystalline ceramics |
| CN110642232A (en) * | 2019-09-26 | 2020-01-03 | 中机第一设计研究院有限公司 | Optimized N-type Bi2Te3Method for organizing and characterizing a thermoelectric material |
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| CN102154692B (en) * | 2011-02-25 | 2012-07-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of In-Se-based thermoelectric material |
| CN102154692A (en) * | 2011-02-25 | 2011-08-17 | 中国科学院宁波材料技术与工程研究所 | Preparation method of In-Se-based thermoelectric material |
| CN103058152A (en) * | 2013-01-16 | 2013-04-24 | 吉林大学 | Non-bismuth-telluride-doped magnetic material and preparation method thereof |
| CN103101887A (en) * | 2013-02-07 | 2013-05-15 | 浙江工业大学 | Bi3Se4 nanobelt and application of Bi3Se4 nanobelt as thermoelectric material |
| CN103101887B (en) * | 2013-02-07 | 2014-08-27 | 浙江工业大学 | Bi3Se4 nanobelt and application of Bi3Se4 nanobelt as thermoelectric material |
| CN104393163B (en) * | 2014-10-09 | 2017-11-28 | 广东先导稀材股份有限公司 | A kind of preparation method of tellurium bismuthino thermoelectric material |
| CN104393163A (en) * | 2014-10-09 | 2015-03-04 | 广东先导稀材股份有限公司 | Preparation method of bismuth telluride-based thermoelectric material |
| CN104831344A (en) * | 2015-04-29 | 2015-08-12 | 河南鸿昌电子有限公司 | Crystal pulling method of semiconductor crystal bar |
| CN105047809A (en) * | 2015-06-30 | 2015-11-11 | 中国科学院宁波材料技术与工程研究所 | SnSe-based thermoelectric material and preparation method thereof |
| CN105047809B (en) * | 2015-06-30 | 2018-06-05 | 中国科学院宁波材料技术与工程研究所 | SnSe base thermoelectricity materials and preparation method thereof |
| CN109095916A (en) * | 2018-08-14 | 2018-12-28 | 徐州市江苏师范大学激光科技有限公司 | A kind of method that SPS sintering prepares YAG crystalline ceramics |
| CN110642232A (en) * | 2019-09-26 | 2020-01-03 | 中机第一设计研究院有限公司 | Optimized N-type Bi2Te3Method for organizing and characterizing a thermoelectric material |
| CN112342617A (en) * | 2020-09-30 | 2021-02-09 | 浙江先导热电科技股份有限公司 | Bismuth telluride zone-melting ingot casting mold and using method thereof |
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