CN1333093C - Preparation method of bismuth-tollurium base thromoelectric alloy - Google Patents
Preparation method of bismuth-tollurium base thromoelectric alloy Download PDFInfo
- Publication number
- CN1333093C CN1333093C CNB2005101233033A CN200510123303A CN1333093C CN 1333093 C CN1333093 C CN 1333093C CN B2005101233033 A CNB2005101233033 A CN B2005101233033A CN 200510123303 A CN200510123303 A CN 200510123303A CN 1333093 C CN1333093 C CN 1333093C
- Authority
- CN
- China
- Prior art keywords
- ball milling
- alloy
- powder
- bismuth
- tollurium
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention belongs to the technical field of thermoelectric material, which relates to thermoelectric alloy and a preparation method thereof. The preparation method of bismuth-tellurium base thermoelectric material of the present invention has the steps of mixing, smelting rapid quenching, powdering, ball milling, compaction and machine work. Simple substances are made into alloy via a vacuum melting method, smelting temperature is 500 to 750 DEG C, and smelting time is 10 to 20 hours. The present invention can carry out metamictizing processes via a cold quenching method. The present invention can carry out ball milling to the obtained amorphous alloy after smelting, ball milling time is 2 to 20 hours, and the ratio of ball and material is 5: 1 to 10: 1. With vacuum or inert gas protection, obtained powder after vacuum drying can be provided with hot pressing or hot shearing extrusion processes, hot pressing temperature is 350 to 550 DEG C, heating rate is 150 to 500 DEG C/ h, hot pressing time is 30 to 90 min, and pressure is 30 to 150MPa. The temperature of the hot shearing extrusion is 400 to 550 DEGC, and extrusion ratio is 1.2 to 4. The method can produce semiconductor thermoelectric alloy with high density and high thermoelectric optimum value, the method can greatly increase material utilization, machinability and product reliability, production cost is greatly reduced, and the method has excellent industrial foreground.
Description
Technical field
The invention belongs to the thermoelectric material field, relate to electrothermal alloy and preparation method thereof.
Background technology
Thermoelectric material is a kind of functional materials that heat energy and electric energy can be transformed mutually, because the application that is found to be thermoelectric energy transmodulator and thermoelectric refrigeration of Seebeck effect and paltie effect provides theoretical basis.The quality of pyroelectric material performance is mainly characterized by thermoelectric figure of merit Z, and Z defines with following formula: Z=α
2σ/k, wherein α is the Seebeck coefficient, and σ is a specific conductivity, and k is a thermal conductivity, and the Z value is big more, and the thermoelectric transformation efficiency of material is high more.Therefore the ideal thermoelectric material should be the alloy material with high as far as possible Seebeck coefficient, high conductivity, lower thermal conductivity.Thermal conductivity reduces along with reducing of grain-size, and specific conductivity increases along with the minimizing of the crystal grain quantity that flows through electric current.If the thermoelectric material density of preparation is not high, wherein exist hole fine and close inadequately, conductivity of electrolyte materials is descended significantly, the thermoelectric figure of merit Z of material decreases.Increase along with thermoelectric material density, conductivity of electrolyte materials also can increase thereupon, this moment, specific conductivity will be higher than the influence of thermal conductivity to the influence of conducting material thermoelectricity performance though thermal conductivity also can increase thereupon, so the thermoelectric figure of merit Z of semiconductor material can increase along with the increase of density.The total shortcoming of the thermoelectric material of being invented was that the intensity of material is low in the past, and fragility is big, and machinability is poor, and this makes the application of thermoelectric material be subjected to very big restriction.Density has remarkable influence for the intensity of thermoelectric material, and along with the ultimate compression strength of the increase thermoelectric material of density of material, bending strength all can increase significantly.Bi
2Te
3The thermoelectricity capability of compound is an anisotropy, along different its thermoelectricity capabilities of grain growing direction bigger variation is arranged.Be the best at the direction of growth thermoelectricity capability that is parallel to crystal grain.Bi-Te based compound and solid solution alloy thereof are that present commercial application is the most extensive, the best room temperature type thermoelectric material of performance.The occasion low at various refrigeration temperatures, that cooling load is less has wide application prospect.
Thermoelectric material has no mechanical moving parts, noiseless, nothing wearing and tearing, simple in structure, advantage such as the volume shape can design on demand.Can be applicable to numerous areas such as petrochemical complex, detecting instrument, environmental protection, aerospace, health care, household electrical appliance.
The multiple preparation method of Bi-Te base thermoelectricity material is disclosed in the prior art.At publication number is in the Chinese patent of CN1488572A, mentions the method that adopts zone melting method and discharge plasma sintering legal system to be equipped with bismuth telluride-base thermoelectric material, and the powder that this method adopts is the Bi by the zone melting method preparation
2Te
3Polycrystalline rod is pulverized and is made, adopt the plasma discharging Fast Sintering then, this sintering process is shorter than the method time of normal sintering, therefore grain-size is less, help the raising of product mechanical property, but because sintering time is too short, the densification process in the powder is affected, inaccessible higher density.At publication number is in the Chinese patent of CN1426120A, mention the method that adopts upset method hot extrusion technology to prepare the Bi-Te base thermoelectricity material, this method adopts the alloy of vacuum melting to pulverize and makes powder, carry out the hot extrusion of upset formula then, make goods have degree of grain alignment preferably, but the powder that this method adopts is not a fast quenching refrigerative amorphous powder, and the grain-size of goods is grown up in hot extrusion process, makes the thermoelectricity capability of goods be under some influence.In United States Patent (USP) 6440768, propose to adopt vacuum melting to produce the method that powdered alloy combines with discharge plasma sintering and prepare thermoelectric material.This method and above-mentioned Chinese publication number are that the sintering technology of CN1488572A is identical, therefore also have same shortcoming.
Summary of the invention
The object of the present invention is to provide a kind of bismuth-tollurium base thromoelectric preparation methods, the bismuth-tollurium base thromoelectric material that this method is prepared, not only thermoelectric figure of merit height, density height, and machining property excellence, technology advanced person.
At above-mentioned purpose, the preparation method of Bi-Te base thermoelectricity material of the present invention adopts powder metallurgic method, and its processing step comprises batching, melting fast quenching, pulverizing and ball milling, compression moulding and machining, and existing division is as follows:
(1) batching
The preparation of Bi-Te base thermoelectricity material of the present invention is a raw material with high-purity Bi, Te, Sb, Se element powder, prepares burden by following chemical formula, and its chemical formula is:
(Bi
2Te
3)
x(Sb
2Te
3)
y(Bi
2Se
3)
zX+y+z=100% wherein; X, y, z value are 0～1.
(2) melting fast quenching
Pack in silica tube being equipped with good raw material powder, and seal vacuum tightness＞10 after vacuumizing or charge into rare gas element
-2Pa, rare gas element be in argon gas or the nitrogen any.
The silica tube of encapsulation raw material powder is placed the resistance furnace melting, and smelting temperature is 500～750 ℃, and smelting time is 10～20h, and the molten mass after the melting makes molten mass form amorphous alloy by the method for chilling fast quenching; The speed of cooling of chilling fast quenching＞10
5℃/second.
(3) pulverizing and ball milling
The amorphous alloy that the melting fast quenching obtains places mortar to pulverize earlier, puts into the ball mill ball milling afterwards again, and adds the hexanaphthene grinding aid; The ball milling time is 2～20h, and ratio of grinding media to material is 5: 1～10: 1, and the powder of gained is clean with alcohol wash behind the ball milling, and dry under the vacuum; The granularity of powder is 5～300 μ m.
(4) compression moulding
The powder that ball milling is obtained has carried out hot pressing or hot shearing extruding under vacuum or protection of inert gas; so that obtain having the semiconductor alloy of good dies orientation; 350～550 ℃ of hot pressing temperatures; pressure is 30～150MPa; hot pressing time 30～90 minutes; 150～500 ℃/hour of temperature rise rates, mould are graphite jig.The temperature of hot shearing extruding is 400～550 ℃, and extrusion ratio is 1.2～4.0.No matter be hot pressing or hot shearing extruding, can finally realize obtaining the alloy of high-density and height grain orientation structure by pressure process repeatedly.
(5) machining
The Bi-Te base thermoelectricity material block elements of hot pressing or hot shearing extruding compression moulding is carried out the line cutting, obtain the Bi-Te based thermoelectric alloy material of user's desired size.
The prepared Bi-Te base electrothermal alloy of the present invention has excellent performance, and its orientation factor F is 0.2～1.2, and the thermoelectric figure of merit of n type sample is 2.2 * 10
-3～2.9 * 10
-3K
-1, the thermoelectric figure of merit of P type sample is 2.8 * 10
-3～3.5 * 10
-3K
-1
The preparation method of Bi-Te base thermoelectricity material of the present invention is a kind of thermoelectric material preparation method of optimization.This method adopts vacuum melting fast quenching method of cooling to make non-crystaline amorphous metal, make ultrafine powder after crushed as initial powder, this powder is the ultra-fine state of amorphous, make the heat treatment process in later stage, crystal grain can remain on tiny size, helps improving the thermoelectricity capability of goods like this and obtains high density.Simultaneously, the preparation method of sintering process is simple, is easy to control, and material preparation process is easy to the formation scale, and the mechanical property of goods is good, is easy to be machined to bigger length-to-diameter ratio.
Compared with prior art, the present invention has following advantage:
(1) compare with the ingot casting of melting, the agglomerating sample has more dislocation, lattice imperfection after the post forming, has effectively reduced phonon transmission in the material, has reduced lattice thermal conductivity, and thermal conductivity reduces the thermoelectric figure of merit that can improve goods.
(2) hot pressing of the present invention's employing and hot shearing are pushed, and help improving the orientation degree of grain structure, and the density that further improves goods.It is good to have the products machinery performance, and the advantage that can manufacture.
(3) preparation method of sintering process is simple, is easy to control, and material preparation process is easy to the formation scale.
(4) mechanical property of goods is good, is easy to be machined to bigger length-to-diameter ratio.
Embodiment
Now the invention will be further described in conjunction with the embodiments.
Example one:
With purity is 99.999% Bi powder and Te powder, presses Bi
2Te
3The mixed of chemical formula proportioning, in the silica tube of packing into, sealed after being vacuumized, vacuum tightness are 1 * 10
-3Pa.
Place resistance furnace to carry out melting the silica tube of charging feedstock, 500 ℃ of smelting temperatures, insulation 10h stirred once every two hours, made melting even, took out the chilling fast quenching.The fast quenching speed of cooling is 1 * 10
5℃/sec.
The non-crystalline state sheet strip that the melting fast quenching is obtained smashes in mortar, puts into the ball mill ball milling again, adopts ceramic pot and Ceramic Balls, and ratio of grinding media to material is 5: 1, and the ball milling time is 3 hours, and the powder that obtains uses alcohol to rinse well, carries out vacuum-drying.
The powder that makes is packed in the graphite jig, place sintering oven again, with vacuum hotpressing the powder that makes is carried out double sintering, sintering temperature is 350 ℃, pressure 30MPa, sintering time 30min, heat-up rate is 150 ℃/hour, makes the block materials of φ 60 * 20 behind the sintering, adopts line to cut specimen, Seebeck coefficient, specific conductivity specimen are of a size of 2 * 2 * 17, and the thermal conductivity specimen is of a size of φ 12 * 2.Afterwards the performance of sample is tested, test result is listed table 1 in.
Embodiment two.
With purity is 99.999% Bi powder, Te powder, Sb powder, presses chemical formula (Bi
2Te
3)
0.2(Sb
2Te
3)
0.8Atomic percent example mix, in the silica tube of packing into, seal after charging into rare gas element Ar gas.
The silica tube of sealing raw material places resistance furnace to carry out melting, and smelting temperature is 670 ℃, and insulation 15h stirred once every two hours, made melting even, takes out the chilling fast quenching after the melting rapidly, and the fast quenching speed of cooling is 1.2 * 10
5℃/sec.
The non-crystalline state sheet strip that the melting fast quenching is obtained smashes in mortar, puts into the ball mill ball milling again, adopts ceramic pot and Ceramic Balls, and ratio of grinding media to material is 7: 1, and the ball milling time is 3.2 hours, and the powder that obtains uses alcohol to rinse well, carries out vacuum-drying.
The powder that makes is packed in the graphite jig, place sintering oven again, with vacuum hotpressing the powder that makes is carried out double sintering, hot pressing temperature is 460 ℃, pressure 150MPa, sintering time 50min, heat-up rate are 250 ℃/hour, make block materials behind the sintering, the size of block materials is identical with embodiment one with line cutting specimen size.Afterwards the performance of sample is tested, test result is listed table 1 in.
Embodiment three.
With purity is 99.999% Bi powder, Te powder, Se powder, presses chemical formula (Bi
2Te
3)
0.975(Bi
2Se
3)
0.025Atomic percent example mix, in the silica tube of packing into, sealed after being vacuumized, vacuum tightness are 1 * 10
-3Pa.
The silica tube of sealing raw material places resistance furnace to carry out melting, 730 ℃ of smelting temperatures, and insulation 12h stirred once every two hours, made melting even, took out the chilling fast quenching after the melting rapidly, and the fast quenching speed of cooling is 1.2 * 10
5℃/sec.
The non-crystalline state sheet strip that the melting fast quenching is obtained smashes in mortar, puts into the ball mill ball milling again, adopts ceramic pot and Ceramic Balls, and ratio of grinding media to material is 10: 1, and the ball milling time is 20 hours, and the powder that obtains uses alcohol to rinse well, carries out vacuum-drying.
The powder that makes is packed in the graphite jig, place sintering oven again, with vacuum hotpressing the powder that makes is carried out double sintering, sintering temperature is 550 ℃, pressure 50MPa, sintering time 90 minutes, heat-up rate are 480 ℃/hour, make block materials behind the sintering, the block materials size is identical with embodiment one with line cutting specimen size.Afterwards the performance of sample is tested, test result is listed table 1 in.
Embodiment four.
With purity is 99.999% Bi powder, Te powder, Sb powder, presses chemical formula (Bi
2Te
3)
0.2(Sb
2Te
3)
0.8Atomic percent example mix, in the silica tube of packing into, and seal after charging into rare gas element Ar gas.
The silica tube of sealing raw material places resistance furnace to carry out melting, 650 ℃ of smelting temperatures, and insulation 14h stirred once every two hours, made melting even, took out cold quenching.The fast quenching speed of cooling is 1.1 * 10
5℃/sec.
The non-crystalline state sheet strip that the melting fast quenching is obtained smashes in mortar, puts into the ball mill ball milling again, adopts ceramic pot and Ceramic Balls, and ratio of grinding media to material is 6: 1, and the ball milling time is 9 hours, and the powder that obtains uses alcohol to rinse well, carries out vacuum-drying.
The powder that makes packed into adopt in the graphite jig hot shearing extruding that the powder that makes is carried out double sintering, extrusion temperature is 400 ℃, and extruding heat temperature raising speed is 150 ℃/hour, extrusion ratio 1.4.Make the block materials of φ 40 * 50 after the hot shearing extruding.From block materials center line cutting specimen, sample size is identical with embodiment one.Afterwards the performance of sample is tested, test result is listed table 1 in.
Embodiment five.
With purity is 99.999% Bi powder, Te powder, Se powder, presses chemical formula (Bi
2Te
3)
0.975(Bi
2Se
3)
0.025Atomic percent example mix, in the silica tube of packing into, and seal after charging into inert nitrogen gas.
Place resistance furnace to carry out melting the silica tube of sealing raw material, 680 ℃ of smelting temperatures, insulation 10h stirred once every two hours, made melting even, took out cold quenching.The fast quenching speed of cooling is 1.3 * 10
5℃/sec.
The non-crystalline state sheet strip that the melting fast quenching is obtained smashes in mortar, puts into the ball mill ball milling again, adopts ceramic pot and Ceramic Balls, and ratio of grinding media to material is 8: 1, and the ball milling time is 15 hours, and the powder that obtains uses alcohol to rinse well, carries out vacuum-drying.
The powder that makes is packed in the graphite jig, adopt the vacuum hot extrusion that the powder that makes is carried out double sintering, extrusion temperature is 530 ℃, and extruding heat temperature raising speed is 150 ℃/hour, extrusion ratio 3.6.Make the block materials of φ 40 * 50 after the hot extrusion.From block materials center line cutting specimen, sample size is identical with embodiment one.Afterwards the performance of sample is tested, test result is listed table 1 in.
Table 1 embodiment properties of sample test result
| Embodiment | Seebeck factor alpha μ V/K | Specific conductivity ρ * 10 -5Ωm | Thermal conductivity κ W/mK | Thermoelectric figure of merit Z * 10 -3/K | Relative density % | Orientation factor F | Semiconductor type |
| One | 212 | 1.40 | ?1.07 | ?3.00 | ?99 | ?0.8 | ?p |
| Two | 211 | 0.99 | ?1.05 | ?4.28 | ?99.5 | ?0.81 | ?p |
| Three | -188 | 1.01 | ?1.11 | ?3.15 | ?99.5 | ?0.75 | ?n |
| Four | 204 | 0.82 | ?1.19 | ?4.26 | ?104 | ?0.88 | ?p |
| Five | -201 | 0.92 | ?1.04 | ?4.22 | ?102 | ?0.85 | ?n |
Claims (3)
1. the preparation method of a bismuth-tollurium base thromoelectric alloy is characterized in that processing step comprises batching, melting fast quenching, pulverizing and ball milling, compression moulding and machining:
(1) batching
The preparation of bismuth-tollurium base thromoelectric material is a raw material with high-purity Bi, Te, Sb, Se element powder, prepares burden by following chemical formula, and its chemical formula is:
(Bi
2Te
3)
x(Sb
2Te
3)
y(Bi
2Se
3)
z
X+y+z=100% wherein, x, y, z value are 0～1;
(2) melting fast quenching
Pack in the silica tube being equipped with good raw material powder, seal after vacuumizing or charge into rare gas element, this silica tube is placed the resistance furnace melting, smelting temperature is 500～750 ℃, smelting time is 10～20h, and the molten mass after the melting makes molten mass form amorphous alloy by the method for chilling fast quenching; The speed of cooling of chilling fast quenching＞10
5℃/second;
(3) pulverizing and ball milling
The amorphous alloy that the melting fast quenching obtains places mortar to pulverize earlier, puts into the ball mill ball milling afterwards again, and adds conventional grinding aid; The ball milling time is 2～20h, and ratio of grinding media to material is 5: 1～10: 1, and the powder of gained is clean with alcohol wash behind the ball milling, and dry under the vacuum;
(4) compression moulding
The powder that ball milling is obtained carries out hot pressing or hot shearing extruding under vacuum or protection of inert gas, so that obtain having the semiconductor alloy of good dies orientation, 350～550 ℃ of hot pressing temperatures, pressure is 30～150MPa, hot pressing time 30～90 minutes, 150～500 ℃/hour of temperature rise rates, mould are graphite jig; The temperature of hot shearing extruding is 400～550 ℃, and extrusion ratio is 1.2～4.0; No matter be hot pressing or hot shearing extruding, all realize final high-density and the grain orientation structure highly that obtains alloy by pressure process repeatedly;
(5) machining
The bismuth-tollurium base thromoelectric material product of hot pressing or hot shearing extruding compression moulding is carried out the line cutting, obtain the bismuth-tollurium base thromoelectric alloy material of user's desired size.
2. bismuth-tollurium base thromoelectric preparation methods according to claim 1 is characterized in that the granularity of the powder of gained behind the ball milling is 5～300 μ m.
3. bismuth-tollurium base thromoelectric preparation methods according to claim 1 is characterized in that packing in the silica tube being equipped with good raw material powder, seals institute's suction＞10 before the sealing after vacuumizing or charge into rare gas element
-2Pa, the rare gas element that charges into be in argon gas or the nitrogen any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101233033A CN1333093C (en) | 2005-11-17 | 2005-11-17 | Preparation method of bismuth-tollurium base thromoelectric alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101233033A CN1333093C (en) | 2005-11-17 | 2005-11-17 | Preparation method of bismuth-tollurium base thromoelectric alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1757774A CN1757774A (en) | 2006-04-12 |
| CN1333093C true CN1333093C (en) | 2007-08-22 |
Family
ID=36703340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101233033A Expired - Fee Related CN1333093C (en) | 2005-11-17 | 2005-11-17 | Preparation method of bismuth-tollurium base thromoelectric alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1333093C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456877B (en) * | 2013-06-25 | 2016-01-27 | 陈志明 | For freezing or heating the N type semiconductor element manufacture method of device |
| CN103553000B (en) * | 2013-10-26 | 2015-09-30 | 西南交通大学 | Preparation topological insulator Bi 2se 3with perovskite oxide La 0.7sr 0.3mnO 3the method of composite structure |
| 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 |
| CN104555950B (en) * | 2015-01-30 | 2017-02-22 | 中国科学院上海硅酸盐研究所 | Bismuth telluride material with excellent thermoelectric properties at medium temperature zone and method for preparing bismuth telluride material with excellent thermoelectric properties at medium temperature zone |
| CN110098310B (en) * | 2018-01-30 | 2023-11-14 | 中国科学院宁波材料技术与工程研究所 | Preparation method of SnSe-based thermoelectric material oriented polycrystal |
| 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 |
| CN110752285A (en) * | 2019-11-05 | 2020-02-04 | 南方科技大学 | Manufacturing method for improving performance of N-type Bi-Sb-Te-Se-based thermoelectric material |
| 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 |
| CN113333698B (en) * | 2021-05-31 | 2023-04-18 | 东北大学秦皇岛分校 | Completely amorphous lead telluride-based alloy strip and preparation method thereof |
| CN114210978A (en) * | 2021-12-22 | 2022-03-22 | 中国电子科技集团公司第十八研究所 | Hot extrusion molding method of bismuth telluride thermoelectric material |
| CN114408874B (en) * | 2022-01-12 | 2023-07-18 | 深圳热电新能源科技有限公司 | Bismuth telluride thermoelectric material based on entropy engineering and preparation method thereof |
| CN114477102B (en) * | 2022-01-20 | 2023-06-09 | 深圳热电新能源科技有限公司 | N-type bismuth telluride-based thermoelectric material and preparation method and application thereof |
| CN115521146B (en) * | 2022-08-25 | 2023-10-13 | 上海申和投资有限公司 | Preparation method of bismuth telluride thermoelectric bar |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08111546A (en) * | 1994-10-11 | 1996-04-30 | Yamaha Corp | Thermoelectric material and thermoelectric transducer |
| CN1148735A (en) * | 1995-12-10 | 1997-04-30 | 浙江大学 | Method for production of semi-conductor thermoelectric material and apparatus thereof |
| JP2000332307A (en) * | 1999-05-18 | 2000-11-30 | Yamaha Corp | Manufacture of thermoelectric material |
| CN1280706A (en) * | 1997-10-24 | 2001-01-17 | 住友特殊金属株式会社 | Thermoelectric transducing material and method of producing the same |
| JP2001250990A (en) * | 1996-07-03 | 2001-09-14 | Yamaha Corp | Thermoelectric material and its manufacturing method |
| US6307143B1 (en) * | 1998-10-22 | 2001-10-23 | Yamaha Corporation | Thermoelectric materials and thermoelectric conversion element |
| US6458319B1 (en) * | 1997-03-18 | 2002-10-01 | California Institute Of Technology | High performance P-type thermoelectric materials and methods of preparation |
| CN1384048A (en) * | 2002-06-21 | 2002-12-11 | 清华大学 | Nano level metal telluride preparing process |
| JP2003037302A (en) * | 2001-07-23 | 2003-02-07 | Yamaha Corp | Method for manufacturing thermoelectric material |
| CN1426120A (en) * | 2001-12-13 | 2003-06-25 | 雅马哈株式会社 | Thermoelectric material and its preparing method |
-
2005
- 2005-11-17 CN CNB2005101233033A patent/CN1333093C/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08111546A (en) * | 1994-10-11 | 1996-04-30 | Yamaha Corp | Thermoelectric material and thermoelectric transducer |
| CN1148735A (en) * | 1995-12-10 | 1997-04-30 | 浙江大学 | Method for production of semi-conductor thermoelectric material and apparatus thereof |
| JP2001250990A (en) * | 1996-07-03 | 2001-09-14 | Yamaha Corp | Thermoelectric material and its manufacturing method |
| US6458319B1 (en) * | 1997-03-18 | 2002-10-01 | California Institute Of Technology | High performance P-type thermoelectric materials and methods of preparation |
| CN1280706A (en) * | 1997-10-24 | 2001-01-17 | 住友特殊金属株式会社 | Thermoelectric transducing material and method of producing the same |
| US6307143B1 (en) * | 1998-10-22 | 2001-10-23 | Yamaha Corporation | Thermoelectric materials and thermoelectric conversion element |
| JP2000332307A (en) * | 1999-05-18 | 2000-11-30 | Yamaha Corp | Manufacture of thermoelectric material |
| JP2003037302A (en) * | 2001-07-23 | 2003-02-07 | Yamaha Corp | Method for manufacturing thermoelectric material |
| CN1426120A (en) * | 2001-12-13 | 2003-06-25 | 雅马哈株式会社 | Thermoelectric material and its preparing method |
| CN1384048A (en) * | 2002-06-21 | 2002-12-11 | 清华大学 | Nano level metal telluride preparing process |
Non-Patent Citations (1)
| Title |
|---|
| SPS法制备p-型四元Al-Bi-Sb-Te合金的微结构与热电性能 崔教林 等，中国有色金属学报，第15卷第10期 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1757774A (en) | 2006-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1333093C (en) | Preparation method of bismuth-tollurium base thromoelectric alloy | |
| CN100391021C (en) | Ag-Pb-Sb-Te thermoelectric materials and preparation process thereof | |
| CN100377378C (en) | Method for preparing Bi-Sb-Te series thermoelectric material | |
| CN111848165B (en) | P-type bismuth telluride thermoelectric material and preparation method thereof | |
| CN101693962B (en) | Method for preparing p-type filling type skutterudite compound thermoelectric material | |
| CN113735582A (en) | Preparation method of bismuth telluride-based thermoelectric material | |
| CN1974079A (en) | Process of preparing bismuth telluride-base thermoelectric material | |
| CN104555950A (en) | Bismuth telluride material with excellent thermoelectric properties at medium temperature zone and method for preparing bismuth telluride material with excellent thermoelectric properties at medium temperature zone | |
| CN101082114B (en) | Middle-low temperature pseudo-binary electrothermal alloy and preparation process | |
| CN101478026A (en) | Thermoelectric compounds and preparation thereof | |
| CN103864026B (en) | Cu-In-Zn-Te quaternary p-type thermoelectric semiconductor and preparation technology thereof | |
| CN1962416A (en) | Preparation process of bismuth telluride base thermoelectrical material | |
| CN102383023B (en) | Preparation method for ferro-silico-manganese alloy thermoelectric material | |
| CN113421959B (en) | N-type bismuth telluride-based room temperature thermoelectric material and preparation method thereof | |
| CN101338386B (en) | Method for preparing TiNi Sn based thermoelectric compounds | |
| CN105244435B (en) | A kind of new n type thermoelectric materials NbVTaCoSb and preparation method thereof | |
| CN102650005A (en) | High-pressure synthesis preparation method of high-performance densification filled skutterudite thermoelectric material | |
| CN103320666B (en) | Ag-In-Zn-Se quaternary thermoelectric semiconductor and preparation technology thereof | |
| CN104843654A (en) | P-type Ga-Cd-S-Te quaternary compound medium-temperature thermoelectric alloy and preparation process thereof | |
| CN101857928A (en) | P-type Zn4Sb3 based thermoelectric material and preparation method thereof | |
| CN101307392B (en) | Process for preparing CoSb3-based thermoelectric material by combining liquid quenching and spark plasma sintering | |
| CN111334685B (en) | Preparation method of high-density Half-Heusler thermoelectric material and obtained product | |
| CN106981564B (en) | P-type Ag3In7Te12Base high temperature thermoelectric material and its preparation process | |
| CN111162160A (en) | P-type cubic phase Ge-Se-based thermoelectric material and preparation method thereof | |
| CN101345284A (en) | P type europium cadmium stibium based pyroelectric material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: GAUNA BEIJING INSTITUTE OF TECHNOLOGY CO. Free format text: FORMER OWNER: IRON AND STEEL RESEARCH GEUERAL INST. Effective date: 20080606 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080606 Address after: Beijing City, Haidian District Daliushu Village No. 19 Patentee after: BEIJING CISRI-GAONA MATERILALS & TECHNOLOGY Co., LTD. Address before: No. 76, South College Road, Beijing, Haidian District Patentee before: Central Iron & Steel Research Institute |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070822 Termination date: 20131117 |