CN114561706A - Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof - Google Patents
Method for recycling bismuth telluride crystal bar processing waste and utilization method thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 71
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 65
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 60
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000012545 processing Methods 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 21
- 238000005520 cutting process Methods 0.000 claims description 19
- 238000000498 ball milling Methods 0.000 claims description 16
- 238000004857 zone melting Methods 0.000 claims description 11
- 238000001192 hot extrusion Methods 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 238000003621 hammer milling Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
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- 229910052714 tellurium Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/12—Single-crystal growth directly from the solid state by pressure treatment during the growth
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
- C30B35/007—Apparatus for preparing, pre-treating the source material to be used for crystal growth
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- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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Abstract
The invention belongs to the field of material recovery, and provides a method for recovering bismuth telluride crystal bar processing waste, which aims to solve the problems that the existing bismuth telluride crystal bar processing waste recovery scheme is divided into multiple steps and multiple procedures to gradually separate and purify single elements, the process is complex, the period is long, the environmental pollution is serious, and the production cost is high; and then ultrasonically cleaning the powder by deionized water and absolute alcohol in sequence, and then drying to obtain the recycled material. Simple process, short period, less environmental pollution and low cost.
Description
Technical Field
The invention belongs to the field of material recovery, and particularly relates to a method for recovering bismuth telluride crystal bar processing waste and a utilization method thereof.
Background
Thermoelectric materials are functional materials capable of directly converting heat energy and electric energy into each other, and are increasingly attracting attention in the current society. Bismuth telluride as a thermoelectric material with optimal thermoelectric performance near room temperature has an irreplaceable position in the process of commercial application, and is widely applied to industries such as optical communication, refrigeration and the like. Currently, the commercial scale production of bismuth telluride materials usually employs uniaxial growth, such as zone melting and thermal extrusion, to obtain single crystal or columnar crystal of bismuth telluride with excellent thermoelectric properties. The bismuth telluride crystal bar obtained by the production method has poor mechanical processing performance, the material utilization rate in the crystal bar cutting process is 80%, the material utilization rate in the wafer cutting process is 80%, and after the Dice are screened to remove defective products, the use utilization rate of one crystal bar is only 51.2%.
As is known, selenium and tellurium belong to rare elements, generally accompany in pyrite, chalcopyrite and other sulfide ores, have extremely small content and high price, and in addition, the cutting loss is large when producing bismuth telluride thermoelectric materials, the material utilization rate is low, so that the raw material cost is high. Therefore, the development of a technology for efficiently recovering the processing waste of the bismuth telluride crystal bar is very important.
At present, the cutting powder or damaged material generated when cutting a bismuth telluride crystal bar, subsequently cutting a wafer and selecting poor Dice is often recovered by performing single element separation and purification by adopting hydrometallurgy or chemical dissolution. The method for extracting Te and Bi has the theoretical basis that Te or Bi elements are oxidized, and then are separated and purified independently, and the recovery scheme is that valuable elements in the bismuth telluride crystal bar processing waste are separated and purified independently, and single element is separated and purified step by step in multiple steps and multiple procedures, so that the method has the advantages of complex process, long period, serious environmental pollution and high production cost.
Disclosure of Invention
In order to solve the problems of complex process, long period, serious environmental pollution and high production cost of the conventional bismuth telluride crystal bar processing waste material recovery scheme that single element is separated and purified step by step in multiple steps and multiple processes, the invention provides the bismuth telluride crystal bar processing waste material recovery method which has the advantages of simple process, short period, small environmental pollution and low cost.
The invention also provides a method for preparing the bismuth telluride crystal rod by utilizing the recycled bismuth telluride crystal rod processing waste.
The invention is realized by the following technical scheme: a method for recycling processing waste of a bismuth telluride crystal bar comprises the following steps:
(1) crushing the bismuth telluride crystal bar processing waste into powder with the particle size less than 200um in a physical impact mode;
the bismuth telluride crystal bar processing waste material is selected from one or more of cutting crystal bars, subsequently cutting wafers and selecting cutting powder or crushing materials generated by poor Dice.
The Dice is a material processed by a nickel layer, a tin layer and the like on the surface of the wafer after cutting.
And respectively recovering N, P type bismuth telluride crystal bar waste materials.
The physical impact mode comprises ball milling, hammer milling and roller milling. Preferably, the ball milling conditions are as follows: the ball material mass ratio is 0.5-5: 1, the ball milling rotation speed is 200-.
The bismuth telluride crystal bar processing waste is crushed into powder, the particle size is reduced by a ball milling mode, the scattering of phonons out of crystal boundaries is increased, and the lattice thermal conductivity is reduced, so that the thermoelectric property of the material is improved.
Preferably, the method includes magnetically adsorbing the powder, and more preferably, magnetically adsorbing the magnetic impurities contained in the processing step by strong magnetism.
(2) And (3) ultrasonically cleaning the powder by deionized water and absolute alcohol in sequence, and then drying to obtain the recycled material.
The drying comprises airing and low-temperature drying. Preferably, the low-temperature drying is vacuum low-temperature drying at the temperature of 50-100 ℃ and the vacuum pressure of 10Pa-50 Pa.
Preferably, the dried powder is further subjected to physical impact means such as ball milling, hammer milling, and roll milling to further grind the powder into nanoscale powder. Preferably, the ball milling conditions are as follows: the ball material mass ratio is 0.5-5: 1, the ball milling rotation speed is 200-.
The recovery rate of valuable elements is above 99%, compared with the traditional method for separating and purifying single element by wet metallurgy, the recovery rate is higher, the economic benefit is better, and the production cost is lower. In addition, the method does not discharge solid wastes and toxic and harmful liquid in the recovery process, is green and environment-friendly, and the discharge of a large amount of solid wastes and toxic liquid in the traditional hydrometallurgy recovery method is difficult to avoid, so the environmental pollution is small.
The material recovered by the method for recovering the processing waste of the bismuth telluride boule is utilized to prepare the bismuth telluride boule, and the preparation method comprises zone melting, powder metallurgy and hot extrusion.
Preferably, the floating zone method comprises the following steps: firstly, carrying out component adjustment on a recovered material, namely reversely deducing the content of each component of a recovered crystal bar by measuring the thermoelectric property of the material, adding an element into the prepared recovered powder to enter the material, regulating the concentration of an internal carrier by adjusting the doping amount of Bi, Te, Sb and the like in an N type or a P type to enable the crystal bar material to reach the optimal performance state near room temperature, putting the crystal bar material into a glass tube, vacuumizing and packaging the glass tube, then putting the glass tube into a heating furnace to smelt the powder, wherein the smelting temperature is 550-800 ℃, more preferably 585-750 ℃, then cooling the powder to the room temperature along with the furnace, and taking out an alloy ingot in the glass tube, namely the bismuth telluride crystal bar.
Preferably, the hot extrusion step is: the method comprises the steps of adjusting the components of a recovered material, namely reversely deducing the content of each component of a recovered crystal bar by measuring the thermoelectric property of the material, adding an element into prepared recovered powder, adjusting the doping amount of Bi, Te, Sb and the like in an N type or a P type to regulate the concentration of internal carriers so that the crystal bar material reaches the best performance state near room temperature for cold press molding, and then performing hot extrusion on the molded powder, wherein the pressure is 50-1000MPa, and the temperature is 200-800 ℃.
zT＝α2σT/κ
According to the formula, there are two general methods for increasing the zT value of the thermoelectric material, one is to increase its power factor (PF ═ α)2σ), or to reduce its thermal conductivity coefficient (κ).
The Seebeck coefficient alpha of the material and the carrier concentration eta in the material body are in a negative correlation; the conductivity σ has a positive correlation with η, so the power factor of the material is tightly coupled with η. And there is an optimum carrier concentration η opt to maximize the corresponding PF.
Through experiments, the P type Bi is found2-xSbxTe3Or N type Bi2-xSbxTe2.7Se0.3The carrier concentration is increased conveniently and easily along with the increase of the Sb content, so that the carrier concentration of the material is increased by adding the additional Sb element, the optimal zT value is obtained, and the performance of the crystal bar at the room temperature can meet the requirement.
The method directly uses the bismuth telluride crystal bar processing waste to prepare the bismuth telluride crystal bar, and prepares the bismuth telluride crystal bar again through impurity removal and cleaning processes, is completely different from the traditional method for separating and purifying single element by wet metallurgy, and has simple recovery process. Experiments show that the N, P type bismuth telluride material is prepared from the processing waste of the bismuth telluride crystal bar to the final stage, the recycling period is only 1.5-10 h, and compared with the production process of the traditional recycling method, the period is greatly shortened.
Compared with the prior art, the invention has the beneficial effects that: has the characteristics of simple process, short recovery period, small environmental pollution and low cost.
Drawings
FIG. 1 shows the EDS composition of untreated bismuth telluride boule processing waste of example 1;
FIG. 2 shows the EDS composition of the impurity-removed bismuth telluride boule processing waste of example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. The starting materials used in the examples are either commercially available or prepared by conventional methods.
Example 1
(1) Crushing processing waste materials of a P-type bismuth telluride crystal bar (including a P-type cutting crystal bar, a subsequent cutting wafer and powder or crushed materials in a poor Dice sorting process) into fine powder with the particle size of 10-100um by using a ball mill, and then adsorbing magnetic impurities in the processing process by using strong magnetism, wherein the mass ratio of ball materials in the ball mill is 3: 1, the ball milling speed is 500r/min, and the ball milling time is 15 min.
(2) Washing with deionized water and absolute ethyl alcohol in sequence, and drying in a vacuum drying oven at 80 deg.C and vacuum pressure of 30Pa to obtain the recovered material.
As shown in fig. 1, the energy dispersive X-ray spectrometer shows that the nickel content on the surface of the untreated bismuth telluride boule waste is high (accounting for 18% of the total components), the nickel content of the treated bismuth telluride boule waste is reduced significantly, and no nickel element can be detected under EDS, as shown in fig. 2.
Preparation example 1
Firstly, putting a small amount of the material which is obtained in the embodiment 1 and is recovered after removing impurities into a glass tube, vacuumizing and packaging the glass tube, putting the glass tube into a heating furnace for smelting at 580-680 ℃, then cooling the glass tube to room temperature along with the furnace, performing zone melting on the cooled and formed crystal bar again at 580-680 ℃, and taking out an alloy ingot in the glass tube after cooling the crystal bar after zone melting to obtain a P-type bismuth telluride crystal bar sample;
firstly, ZEM-3 equipment is adopted to measure the thermoelectric property of a P-type bismuth telluride crystal bar sample, and the carrier concentration is 5x1019cm-3Adjusting Sb doping quantity to regulate internal carrier concentration to enable the crystal bar material Bi to correspond to the Sb content x being 1.42-xSbxTe3The performance requirement is achieved near room temperature, and the Sb content x is 1.6 (corresponding to the carrier concentration of 6x 10)19cm-3) Adding Sb with the content of 0.2 into a glass tube, vacuumizing and packaging the glass tube, smelting in a heating furnace at 580-680 ℃, cooling to room temperature along with the furnace, zone-melting the cooled and formed crystal bar again at 580-680 ℃, cooling after zone-melting, taking out an alloy ingot in the glass tube to obtain the P-type bismuth telluride crystal bar with the carrier concentration of 6x1019cm-3。
The Seebeck coefficient of the P-type bismuth telluride crystal bar is 200 (mu V/K) near room temperature, and the conductivity is 10 (10)4Sm-1)
Example 2
(1) Crushing processing waste materials (including an N-type cutting crystal bar, a subsequent cutting wafer and powder or crushed materials in a poor Dice sorting process) of the bismuth telluride crystal bar into fine powder with the particle size of 100-;
(2) washing with deionized water and absolute ethyl alcohol in sequence, and drying in a vacuum drying oven at 60 deg.C and 20Pa to obtain the recovered material.
Preparation example 2
Firstly, putting a small amount of the material which is obtained in the embodiment 2 and is recovered after removing impurities into a glass tube, then vacuumizing and packaging the glass tube, putting the glass tube into a heating furnace for smelting at the smelting temperature of 650-.
Firstly, measuring the thermoelectric property of an N-type bismuth telluride crystal bar sample by adopting ZEM-3 equipment, wherein the thermoelectric property corresponds to the carrier concentration of 5x1019cm-3Adjusting Sb doping amount to regulate internal carrier concentration to enable the crystal bar material Bi to correspond to the Sb content x being 0.152- xSbxTe2.7Se0.3)The performance requirement is met near room temperature, the Sb content x is 0.18, and the corresponding carrier concentration is 6x1019cm-3And adding Sb with the content of 0.03 into a glass tube, vacuumizing and packaging the glass tube, smelting in a heating furnace at the smelting temperature of 650 plus 720 ℃, cooling to room temperature along with the furnace, zone-melting the cooled and formed crystal bar again at the zone-melting temperature of 650 plus 720 ℃, and taking out an alloy ingot in the glass tube after cooling after zone-melting is finished to obtain the N-type bismuth telluride crystal bar.
The Seebeck coefficient of the N-type bismuth telluride crystal bar is 2 at the temperature near room temperature00 (. mu.V/K), conductivity 10 (10)4Sm-1)。
Example 3
(1) Crushing processing waste materials of the P-type bismuth telluride crystal bar (including the processing waste materials of the bismuth telluride crystal bar, namely powder or crushed materials in the processes of cutting the crystal bar, subsequently cutting a wafer and sorting poor Dice) into fine powder of 10-100um by using a ball mill, adsorbing magnetic impurities in the processing process by using strong magnetism, wherein the mass ratio of ball materials in the ball mill is 5: 1, the ball milling speed is 700r/min, and the ball milling time is 30 min;
(2) washing with deionized water and absolute ethyl alcohol in sequence, placing the mixture into a vacuum drying oven for drying treatment, wherein the temperature is 90 ℃, the vacuum pressure is 40Pa, then further grinding the mixture into 100-fold 500-nanometer powder by using a ball mill, the mass ratio of ball materials in the ball mill is 5: 1, the ball milling speed is 700r/min, and the ball milling time is 30min, thus obtaining the recovered material.
Preparation example 3
Firstly, cold press molding is carried out on a small amount of the material which is obtained in the embodiment 3 and is recovered after impurities are removed, hot extrusion operation is carried out at high temperature and high pressure, and the hot extrusion conditions are as follows: and carrying out hot extrusion on the molded powder under the pressure of 500Mpa at the temperature of 500 ℃ to prepare a P-type extruded crystal bar sample.
Firstly, an ZEM-3 device is adopted to measure the thermoelectric property of a P-type extruded crystal bar sample, and the carrier concentration is 4x1019cm-3Adjusting Sb doping amount to regulate internal carrier concentration to enable the crystal bar material Bi to correspond to the Sb content x being 1.32-xSbxTe3The performance requirement is achieved near room temperature, and the Sb content x is 1.6 (corresponding to the carrier concentration of 6x 10)19cm-3) And the Sb content is required to be added to be 0.3, cold press molding is carried out, hot extrusion operation is carried out at high temperature and high pressure, and the hot extrusion conditions are as follows: hot extruding the formed powder under 500Mpa at 500 deg.C to obtain P-type extruded crystal bar with carrier concentration of 6x1019cm-3。
The Seebeck coefficient of the P-type extruded crystal bar is 200 (mu V/K) and the conductivity is 10 (10) near room temperature4Sm-1)。
Tests show that the recovery rate of valuable elements in the Te, Sb, Se and Bi elements in the bismuth telluride crystal bar processing waste materials recovered in the embodiments 1 to 3 is more than 99 percent, and compared with the traditional method for separating and purifying single element by wet metallurgy, the method has the advantages of higher recovery rate, better economic benefit and lower production cost.
Examples 1-3 preparation of N-type or P-type Bi directly from bismuth telluride boule processing waste2Te3The N-type Bi can be obtained by the two steps of removing impurities and adjusting components in front and back of the base thermoelectric material2Te3The base thermoelectric material is completely different from the traditional method for separating and purifying single elements by wet metallurgy, and the recovery process is simple. The recycling cycle is only 1.5-10 h, and compared with the production process of the traditional recycling method, the cycle is greatly shortened.
Claims (10)
1. A method for recycling processing waste of a bismuth telluride crystal bar is characterized by comprising the following steps:
(1) crushing the bismuth telluride crystal bar processing waste into powder with the particle size of less than 200um in a physical impact mode;
(2) and (3) ultrasonically cleaning the powder by deionized water and absolute alcohol in sequence, and then drying to obtain the recycled material.
2. The method for recycling the processing waste of the bismuth telluride crystal bar as claimed in claim 1, wherein the processing waste of the bismuth telluride crystal bar is selected from one or more of cutting powder or broken powder generated by cutting a crystal bar, subsequently cutting a wafer and sorting poor Dice.
3. The method for recycling the processing waste of the bismuth telluride crystal bar as in claim 1, wherein the physical impact manner in the step (1) comprises ball milling, hammer milling and roller milling.
4. The method for recycling the processing waste of the bismuth telluride crystal bar as in claim 3, wherein the ball milling conditions are as follows: ball-material ratio (0.5-5): 1, the ball milling rotation speed is 200-.
5. The recycling method of bismuth telluride boule processing scrap as in any one of claims 1 to 4 wherein step (1) includes magnetic adsorption of the powder.
6. The method for recycling the bismuth telluride crystal bar processing waste material as in claim 1, wherein the drying in the step (2) comprises airing and low-temperature drying.
7. The method for recycling the processing waste of the bismuth telluride crystal bar as in claim 6, wherein the low-temperature drying is vacuum low-temperature drying at 50-100 ℃ and under a vacuum pressure of 10Pa-50 Pa.
8. The method for preparing the bismuth telluride boule by using the materials recovered by the method for recovering the bismuth telluride boule processing wastes according to claims 1 to 7 is characterized by comprising zone melting, powder metallurgy and hot extrusion.
9. The method for preparing the bismuth telluride crystal bar according to claim 8, wherein the step of the zone melting method is as follows: firstly, the components of the recovered material are adjusted and then put into a glass tube, the glass tube is vacuumized, and then the glass tube is put into a heating furnace to smelt the powder, wherein the smelting temperature is 550-800 ℃.
10. The method for preparing the bismuth telluride boule as in claim 8, wherein the step of hot-extruding comprises: adjusting the components of the recycled material, performing cold press molding, and performing hot extrusion on the molded powder, wherein the pressure is 50-1000Mpa, and the temperature is 200-800 ℃.
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