CN1757774A - Preparation method of bismuth-tollurium base thromoelectric alloy - Google Patents
Preparation method of bismuth-tollurium base thromoelectric alloy Download PDFInfo
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Abstract
A process for preparing the BiTe-based electrothermal material includes such steps as proportionally mixing raw materials, vacuum smelting for alloying, quick cold quenching for non-crystalline treating, breaking, ball grinding, vacuum drying, hot pressing or hot shear extruding and machining. Its advantages are high density, thermoelectric performance, and machinability and low cost.
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 advanced powder metallurgic method, and its processing step comprises batching, melting fast quenching, pulverizing and ball milling, compacting 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 element powder such as high-purity Bi, Te, Sb, Se, 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
Be packaged in the 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 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 carries out the hot pressing of hyperpressure or hot shearing extruding so that obtain having the semiconductor alloy of good dies orientation under vacuum or protection of inert gas; 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 hyperpressure 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 superfine 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) the present invention adopts the hot pressing and the hot shearing extruding of ultra-high voltage, helps 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. bismuth-tollurium base thromoelectric preparation methods is characterized in that processing step comprises batching, melting fast quenching, pulverizing and ball milling, compacting and machining:
(1) batching
The preparation of bismuth-tollurium base thromoelectric material of the present invention is a raw material with element powder such as high-purity Bi, Te, Sb, Se, 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
Be packaged in the silica tube being equipped with good raw material powder, and 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, 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 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 the hot pressing or the shear extrusion of hyperpressure under vacuum or protection of inert gas; to 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 hyperpressure hot pressing or hot shearing extruding, can pass through repeatedly pressure process and realize final high-density and the grain orientation structure highly that obtains alloy.
(5) machining
The Bi-Te base thermoelectricity material goods of hot pressing or hot shearing extruding compression moulding are carried out the line cutting, obtain the Bi-Te based thermoelectric alloy material of user's desired size.
2. the preparation method of Bi-Te base thermoelectricity material 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. the preparation method of Bi-Te base thermoelectricity material according to claim 1 is characterized in that raw material powder is loaded in the silica tube, institute's suction＞10 before the encapsulation
-2Pa, or charge into rare gas element be in argon gas or the nitrogen any.
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|---|---|---|---|
| CNB2005101233033A CN1333093C (en) | 2005-11-17 | 2005-11-17 | Preparation method of bismuth-tollurium base thromoelectric alloy |
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|---|---|---|---|
| CNB2005101233033A CN1333093C (en) | 2005-11-17 | 2005-11-17 | Preparation method of bismuth-tollurium base thromoelectric alloy |
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|---|---|
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| CN1333093C CN1333093C (en) | 2007-08-22 |
Family
ID=36703340
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|---|---|---|---|
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| CN114477102A (en) * | 2022-01-20 | 2022-05-13 | 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 |
| CN115521146A (en) * | 2022-08-25 | 2022-12-27 | 上海申和投资有限公司 | Preparation method of bismuth telluride thermoelectric bar |
| 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 |
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